Pyridine-2,3-dicarboximides, their preparation and their use for controlling undesired plant growth

ABSTRACT

Pyridine-2,3-dicarboximides of the formula I ##STR1## where R 1 , inter alia, is hydrogen or alkoxy; 
     at least one radical R 2 , R 3 , or R 4  is nitro or OR 5  or NR 6  R 7  group; 
     R 5 , inter alia, is hydrogen or C 1  -C 4  -alkylcarbonyl; 
     R 6 , inter alia, is hydrogen or C 1  -C 4  -alkyl; 
     and their agriculturally utilizable salts are described.

The present invention relates to pyridine-2,3-dicarboximides of thegeneral formula I ##STR2## where R¹ is hydrogen;

C₁ -C₄ -alkoxy;

C₁ -C₆ -alkyl which can carry one to three of the following groups:

C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkylthio, C₁ -C₄ -dialkylamino, C₃ -C₈ -cycloalkyl, halogen,excluding C₁ -C₄ -dialkylaminoethyl if one of the radicals R², R³ or R⁴is amino or hydroxyl;

C₃ -C₈ -cycloalkyl, which can carry one to three of the followinggroups: C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkoxy, halogen or nitro;

C₃ -C₆ -alkenyl or C₃ -C₆ -alkynyl, which can be substituted up to threetimes by halogen, and

at least one radical R², R³ or R⁴ is nitro, a group OR⁵ or a group NR⁶R⁷ and the other radicals R², R³ and R⁴ are defined as follows:

i) hydrogen;

ii) halogen, nitro or cyano;

iii) C₁ -C₆ -alkyl, which can be substituted by one to five halogenatoms and/or one or two of the following radicals:

C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkylthio, C₃ -C₆ -cycloalkyl or cyano;

iv) benzyl which can be substituted up to three times by C₁ -C₄ -alkyl,C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -haloalkylthio, halogen, cyano or nitro;

v) C₃ -C₈ -cycloalkyl which can be substituted one to three times by C₁-C₄ -alkyl or halogen;

vi) C₂ -C₆ -alkenyl which can be substituted up to three times byhalogen and/or once by C₁ -C₃ -alkoxy or by phenyl which can carry oneto three of the following groups: C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkylthio, halogen, cyano or nitro;

vii) C₂ -C₆ -alkynyl which can be substituted up to three times byhalogen or C₁ -C₃ -alkoxy and/or once by phenyl which can carry one tothree of the following groups: C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkylthio,halogen, cyano or nitro;

viii) C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkoxy C₁ -C₄-haloalkylthio, C₂ -C₅ -alkenyloxy, C₂ -C₅ -alkynyloxy, C₁ -C₄-alkylsulfinyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄ -haloalkylsulfonyl;

ix) phenoxy or phenylthio which can be substituted up to three times byC₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁-C₄ -alkylthio, C₁ -C₄ -haloalkylthio, halogen, cyano or nitro;

x) a 5- or 6-membered heterocyclic radical having one or two heteroatomsselected from the group consisting of oxygen, sulfur and nitrogen whichcan carry one or two of the following groups: C₁ -C₃ -alkyl, halogen, C₁-C₃ -alkoxy or C₂ -C₄ -alkoxycarbonyl;

xi) phenyl which can carry one to three of the following groups:

C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -haloalkoxy, C₁-C₆ -alkylthio, C₁ -C₆ -haloalkylthio, halogen, nitro or cyano;

xii) a group OR⁵, where R⁵ is hydrogen, C₁ -C₄ -alkylcarbonyl, C₁ -C₄-haloalkylcarbonyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₂ -C₄-alkoxycarbonyl, C₁ -C₄ -alkylcarbamoyl, C₁ -C₄ -dialkylcarbamoyl, C₁-C₄ -alkylsulfonyl, C₁ -C₄ -haloalkylsulfonyl, sulfamoyl, C₁ -C₄-alkylaminosulfonyl, C₁ -C₄ -dialkylaminosulfonyl, phenylsulfonyl, whichcan be substituted one to three times by C₁ -C₄ -alkyl, C₁ -C₄-haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio,halogen, cyano or nitro;

xiii) a group NR⁶ R⁷, where R⁶ is hydrogen, C₁ -C₄ -alkyl, benzyl, C₁-C₄ -alkoxy or, together with R⁷, is C═S and R⁷ is hydrogen, C₁ -C₄-alkyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -haloalkylcarbonyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkoxy-C₂ -C₄ -alkoxycarbonyl, C₁ -C₄-alkylcarbamoyl, C₁ -C₄ -dialkylcarbamoyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄-haloalkylsulfonyl, sulfamoyl, C₁ -C₄ -alkylaminosulfonyl, C₁ -C₄-dialkylaminosulfonyl, phenylsulfonyl, which can be substituted one tothree times by C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkoxy, C₁ -C₄ -alkylthio, halogen, cyano or nitro;

excluding 6-amino-5-cyano-4-phenylpyridine-2,3-dicarboximide;

and their agriculturally utilizable salts.

The invention furthermore relates to processes for preparing thecompounds I and their use for controlling undesired plant growth, andnovel pyridine-2,3-dicarboxylic acid esters andpyridine-2,3-dicarboxylic anhydrides, in particular nitro-substituted ineach case, which are used as intermediates for preparing the compoundsI.

N-substituted pyridinedicarboximides and their derivatives are known.EP-A 128 006 describes, inter alia,N-cycloalkylenepyridinedicarboximides and their use as soil fungicides.

U.S. Pat. No. 3,539,568 describes a process for preparing 2,3- and3,4-pyridinedicarboximides and their reaction to give isomericdicarboxamides which can be used as intermediates for herbicidalpyrimidinediones.

U.S. Pat. No. 4,261,730 describes3-carboxypyridine-2-N-(aryl)carboxamides and phthalamic acids havinggrowth-regulating action.

U.S. Pat. No. 4,658,030 discloses a process for preparing herbicidal2-(imidazolin-2-yl)nicotinic acids based on3-carboxypyridine-2-(N-2-carbamido-3-methyl-2-butyl)carboxamides.

Helv. Chim. Acta 1988, Vol. 71, pp. 486 and 493 discloses acycloaddition process for preparing pyridine-2,3-dicarboximides.

J 5 7085-386 describes specifically substitutedpyridine-2,3-dicarboximides having antitumor action.6-Amino-5-cyano-4-phenylpyridinecarboximide is disclosed in CA 117, 150849.

Herbicidally active pyridine-2,3-dicarboximides are disclosed in EP-A422 456.

Intermediates from the pyridine-2,3-dicarboxylic acid diester group canonly be taken from the prior art in isolated cases. Thus EP-A 227 932describes pyridine-2,3-dicarboxylic acid diesters having the followingsubstitution pattern in the 5/6 position: CH₃ /NO₂, NH₂ /NH₂, NO₂ /Cland NO₂ /NH₂. Dimethyl 4-aminopyidine-2,3-dicarboxylate is known fromChemical Abstracts 111, 112292p (1989), dimethyl or diethyl5-amino-6-methylpyridine-2,3-dicarboxylate from Beilstein No.4-22-006875 (Jones, Am. Soc. 74 (1972), p. 1489). Diethyl 5-acetamido-and 5-methylamino-6-methylpyridine-2,3-dicarboxylates are published inEP-A 322 616. 4-Diethylamino-5-methyl- and5-diethylamino-4-methylpyridine are described in Chemical Abstracts 81,169499c (1974) and 79, 31999t (1973).

It is an object of the present invention to make availablepyridine-2,3-dicarboximides having improved biological activity, inparticular better selectivity or higher herbicidal activity.

We have now found that this object is achieved by thepyridine-2,3-dicarboximides defined at the outset.

Preferred pyridine-2,3-dicarboximides of the formula I are those whereR¹ is hydrogen, C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkynyl,1-(cyclopropyl)-C₁ -C₃ -alkyl, 1-C₁ -C₂ -alkylcyclopropyl or C₃ -C₆-cycloalkyl and two of the three radicals in the pyridine ring R², R³ orR⁴ independently of one another are hydrogen, C₁ -C₄ -alkyl which can besubstituted by one to five halogen atoms, C₁ -C₄ -alkoxy, halogen orcyano, while the third substituent is a nitro group, a group OR⁵, inparticular acetoxy, trifluoroacetoxy or methoxycarbonyl, or a group NR⁶R⁷, in particular amino, methylamino, dimethylamino, acetamido ortrifluoroacetamido.

Particularly preferably, at least one of the radicals R², R³ or R⁴ isnitro or trifluoroacetamido. Compounds having mono- or disubstitution inthe pyridine ring are also preferred. The substituent on the imidenitrogen R¹ is preferably an alkyl radical, in particular a branchedalkyl radical such as i-propyl, sec-butyl or tert-butyl or a1-(cycloalkyl)-C₁ -C₃ -alkyl radical such as 1-(cyclopropyl)methyl,1-(cyclopropyl)ethyl or 1-(cyclopropyl)propyl.

The invention further relates to novel intermediates such as anhydridesand substituted pyridine-2,3-dicarboxylic acid esters. The followingcompounds can be mentioned here:

pyridine-2,3-dicarboxylic anhydrides of the formulae IIa and IIc##STR3## where at least one of the radicals R², R³ or R⁴ is nitro or NR⁶R⁷, and the other radicals have the meanings mentioned at the outset forthe final products I.

Intermediates according to the invention in the dialkyl ester stage arenitro- or amino-substituted dialkyl pyridine-2,3-dicarboxylates of theformulae Va to Vd ##STR4## where R⁵ is a C₁ -C₄ -alkyl, C₃ -C₅ -alkenylor C₁ -C₄ -alkynyl radical, it being possible for the radicals mentionedto be substituted in each case by halogen, in particular one to threehalogen radicals such as fluorine, chlorine or bromine, by C₁ -C₄-alkoxy or by phenyl, and the radicals R² to R⁴ have the followingmeanings:

Va: R⁴ is a nitro group and the radicals R² and R³ have the meaningsmentioned at the outset, as for the final product I;

Vb: R³ is a nitro group and the radicals R² and R⁴ have the meaningsmentioned at the outset, as for the final product I, with the provisothat R² is not methyl, halogen or amino (NH₂) if R⁴ is hydrogen;

Vc: R² is a nitro group and the radicals R³ and R⁴ have the meaningsmentioned at the outset, as for the final product I;

Vd: the radicals R², R³ and/or R⁴ are a group NR⁶ R⁷ and the otherradicals R², R³ or R⁴ have the meanings mentioned at the outset, as forthe final product I, excluding diethyl and dimethyl5-amino-6-methylpyridine-2,3-dicarboxylate, dimethyl4-aminopyridine-2,3-dicarboxylate, diethyl5,6-diaminopyridine-2,3-dicarboxylate, diethyl6-amino-5-nitropyridine-2,3-dicarboxylate, diethyl5-acetamido-6-methylpyridine-2,3-dicarboxylate, diethyl5-methylamino-6-methylpyridine-2,3-dicarboxylate, diethyl4-diethylamino-5-methylpyridine-2,3-dicarboxylate and diethyl6-diethylamino-5-methylpyridine-2,3-dicarboxylate.

The pyridine-2,3-dicarboximides of the formula I can form addition saltswith inorganic acids or with alkyl halides or they can be reacted, ifone of the substituents has acidic properties, with inorganic andorganic bases to give salts. The corresponding salts are likewise a partof the invention.

Suitable basic salts are e.g. those of the alkali metals, preferably thesodium and potassium salts, those of the alkaline earth metals,preferably calcium, magnesium and barium salts, and those of thetransition metals, preferably manganese, copper, zinc and iron salts,and also the ammonium salts which can carry one to three C₁ -C₄ -alkylor hydroxy-C₁ -C₄ -alkyl substituents and/or a phenyl or benzylsubstituent, preferably diisopropylammonium, tetramethylammonium,tetrabutylammonium, trimethylbenzylammonium andtrimethyl-(2-hydroxyethyl)ammonium salts, the phosphonium salts, thesulfonium salts, preferably tri-(C₁ -C₄)-alkylsulfonium salts, and thesulfoxoniumsalts, preferably tri-(C₁ -C₄)-alkylsulfoxonium salts.

If the substitution pattern on the pyridine-2,3-dicarboximide I leads tooptically active compounds, in addition to the racemates the inventionalso includes the (+) and (-) enantiomers.

The pyridine-2,3-dicarboximides of the formula I can be prepared invarious ways, which are described in EP-A 422 456.

According to the invention, pyridine derivatives of the formula I areobtained by reaction of pyridinedicarboxylic anhydrides II ##STR5## inan inert organic solvent with a primary amine III (preferably inapproximately stoichiometric amounts)

    H.sub.2 N--R.sup.1                                         III

to give a pyridinedicarboxylic acid hemiamide IV ##STR6## andcyclization thereof with dehydrating agents to give I.

Additionally, chemically unique processes have been found for preparingthe compounds Ia ##STR7## where R² to R⁴ have the abovementionedmeanings, at least one of the radicals R² to R⁴, two of the radicals R²to R⁴ or all the radicals R² to R⁴ being nitro, by treating pyridinederivatives Ib ##STR8## where R¹ to R⁴ have the abovementioned meanings,at least one of the radicals R² to R⁴ being hydrogen, or two or all ofthe radicals R² to 4 being hydrogen, or the N-oxides of Ib withnitrating agents and if appropriate then removing the N-oxide group.

In the context of the preparation of the compounds according to theinvention, it has furthermore been found that pyridine derivatives ofthe formula Ia are likewise advantageously obtained if the startingmaterials are pyridinedicarboxylic anhydrides of the formula IIb (ortheir N-oxides) ##STR9## where R² to R⁴ have the abovementionedmeanings, at least one of the radicals (namely the radical which isreplaced by nitro), two of the radicals or all the radicals, R² to R⁴,are hydrogen, these are reacted with nitrating agents to givepyridinedicarboxylic anhydrides IIa ##STR10## where R² to R⁴ have theabovementioned meanings, at least one of the radicals, or two or all theradicals, R² to R⁴, being nitro, and this is then converted using asubstituted amine, as described, to the pyridine derivatives Ia.

Preparation of the pyridinedicarboxylic acid hemiamides IV isexpediently carried out by initially introducing the anhydride II in aninert solvent and adding dropwise approximately molar amounts of anamine III, if appropriate likewise dissolved in an inert solvent. Afterreaction is complete, the reaction product is filtered off with suctionor isolated by concentrating the solvent used, the hemiamides IV beingobtained. ##STR11##

Expediently, the solvents used for these reactions are those such ashalohydrocarbons, e.g. tetrachloroethane, methylene chloride,chloroform, chlorobenzene and 1,2-dichlorobenzene; ethers, e.g. diethylether, methyl tert-butyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran and dioxane; dipolar aprotic solvents,e.g. acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone,1,3-dimethyltetrahydro-2(1H)-pyrimidinone and1,3-dimethylimidazolidin-2-one; aromatics, e.g. benzene, toluene,xylene, pyridine and quinoline; ketones, e.g. acetone, methyl ethylketone or appropriate mixtures.

The reaction can be carried out at from -10° C. to the refluxtemperature of the particular solvent or mixture, preferably at from-20° to 120° C.

The molar ratios in which the starting compounds required are reactedwith one another are preferably from 0.9:1 to 3:1 for the ratio of amineIII to anhydride II. The concentration of the starting materials in thesolvent is e.g. from 0.1 to 5 mol/l, preferably from 0.2 to 2 mol/l.

The pyridinedicarboxylic acids or anhydrides required as startingmaterials for this process are commercially available, known from theliterature or can be prepared by generally known methods. A generalsurvey is found in Beilstein H 22, 150-160, E I 531-536, E II 104-111, H27, 261, E I 319, E II 299, R. C. Elderfield, Heterocyclic Compounds,Vol. I, Chapt. 8, J. Wiley and Sons, New York, E. Klingberg, `Pyridineand its Derivatives`, Part 3, Chapt. X, in The Chemistry of HeterocyclicCompounds, 1962, Interscience Publishers, and in EP-A 299 362 and EP-A422 456.

The cyclization of the hemiamides IV is carried out by dehydrating usingcustomary dehydrating agents, for example acetic anhydride or inorganicacid halides, such as thionyl chloride, phosgene, phosphorus trichlorideor pentachloride, to give the pyridine derivatives of the formula I. Thereaction is expediently carried out by initially introducing thecarboxamides in an inert Organic solvent and adding the dehydratingagent dropwise, if appropriate likewise dissolved in an inert solvent.The mixture can be worked up in the customary manner, for example byhydrolysis with water and filtration with suction or extraction of theproduct with an organic solvent and concentration of the organicsolvent: ##STR12##

Expediently, the solvents used for these reactions are those such ashalohydrocarbons, e.g. tetrachloroethane, methylene chloride,chloroform, chlorobenzene and 1,2-dichlorobenzene; ethers, e.g. diethylether, methyl tert-butyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran and dioxane; dipolar aprotic solvents,e.g. acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone,1,3-dimethyltetrahydro-2(1H)-pyrimidinone and1,3-dimethylimidazolidin-2-one; aromatics, e.g. benzene, toluene,xylene, pyridine and quinoline; ketones, e.g. acetone, methyl ethylketone or appropriate mixtures.

The reaction can be carried out at from -10° C. to the refluxtemperature of the particular solvent, preferably at from 0° to 150° C.

The molar ratios in which the starting compounds are reacted with oneanother are in general from 0.9:1 to 5:1 for the ratio of dehydratingagents to acid amide.

The concentration of the starting materials in the solvent (mixture) isin general from 0.1 to 5 mol/l, preferably from 0.2 to 2 mol/l.

A process for preparing compounds Ia where at least one of the radicalsR² to R⁴ is nitro consists in the treatment of a pyridine derivative Ibwith nitrating agents.

The reaction is preferably carried out by treating a pyridine derivativeIb with nitric acid on its own or mixed with sulfuric acid (generallycalled nitrating acid) and if appropriate deoxygenating again. ##STR13##

To carry out the nitration, the pyridine derivative Ib can be dissolvedor suspended in sulfuric acid and nitric acid or nitrating acid added.Occasionally, it is advantageous to introduce the pyridine derivative Ibin initially introduced nitrating acid or nitric acid. The reaction canbe carried out using dilute nitric acid [D: 1.0-1.37), but the use ofconcentrated to fuming nitric acid [D: 1.37-1.52] is more expedient. Ifnitrating acid is used, mixtures of e.g. 20% nitric acid, 60% sulfuricacid and 20% water up to 45% nitric acid and 55% sulfuric acid arecustomarily employed.

An increase in the nitrating action is effected by use of mixtures offuming nitric acid [D: 1.52] with fuming sulfuric acid (oleum). Insteadof sulfuric acid, phosphoric acid or liquid hydrogen fluoride can alsobe used.

Advantageously, the nitration can also be carried out in the presence ofglacial acetic acid. To this end, the pyridine derivative Ib isdissolved or suspended in glacial acetic acid and 60 to 100% strengthnitric acid is added on its own or diluted with glacial acetic acid.

In the case of sensitive substituents, the nitration can also be carriedout in a mixture of acetic acid or trifluoroacetic acid with sodiumnitrate. To this end, the pyridine derivative is suspended together withsodium nitrate in acetic or trifluoroacetic acid and the reaction isthen carried out.

The nitration is particularly preferably made anhydrous in the presenceof acetic acid. In this process, the nitric acid is added to thepyridine derivative Ib dissolved or suspended in acetic anhydride andthe mixture is stirred until the reaction has ended. EXpediently, bothreaction components, pyridine derivative Ib and nitric acid, can bediluted with glacial acetic acid.

At temperatures above 20° C., acetyl nitrate is formed from mixtures ofnitric acid and acetic anhydride.

Instead of acetic anhydride as a solvent, trifluoroacetic anhydride canalso be used. Indifferent solvents which are not attacked by nitric acidunder the particular conditions of the nitration can likewise be used.Aliphatic chlorohydrocarbons such as dichloromethane, chloroform,tetrachloromethane, 1,2-dichloroethane and polychloroethanes arepreferred. Also suitable, however, are gasoline fractions, naphtha,nitromethane, acetonitrile, ethanol, ether, acetone, mono- anddichlorobenzenes and also nitrobenzenes.

The reaction is in general carried out at from -20° to 400° C.,preferably from 0° to 200° C., particularly preferably from 20° to 120°C.

The molar ratios in which the starting compounds required are reactedwith one another are from 0.9:1 to 3.0:1, preferably from 1.1:1 to 1.5:1for the ratio of nitric acid to pyridine derivative Ib. Theconcentration of the starting materials in the solvent is from 0.1 to 5mol/l, preferably from 0.3 to 2 mol/l.

If the reaction is exothermic, a temperature of from 20° to 40° C. isexpediently maintained by cooling during the addition of the first halfof the nitric acid and the cold bath can then be removed withincreasingly gentler course of the reaction. If the extent of reactionis unsatisfactory, it may be necessary to carry the reaction tocompletion by heating, e.g. to 120° C. The reaction time is a quarter ofan hour to 24 hours, depending on the given temperature.

Working up can be carried out in a customary manner, e.g. by filtration,washing the solid material, distillation of filtrate and washfiltration. Advantageously, the pyridine derivatives Ia can beprecipitated in water or ice-water, filtered off with suction, freedfrom acid residues using aqueous alkaline solutions and worked up asdescribed.

The process for preparing the compounds IIa, where at least one of theradicals R² to R⁴ of the abovementioned meanings is nitro, consists inreacting a pyridinecarboxylic anhydride or its N-oxide IIb withnitrating agents and is carried out in the same manner as the reactionof the pyridine derivatives Ib described above. ##STR14##

Instead of at the stage of the pyridinedicarboxylic anhydrides or theirN-oxides IIb, the nitration can also be carried out at the correspondingdiester or N-oxide stage thereof Vb. These can then be converted eitherby hydrolysis to the carboxylic acid salts and cyclization to theanhydrides IIa or reacted directly with the amine III to give carboxylicester hemiamides VI, which, after hydrolysis to IV, can be cyclized togive the compounds Ia according to the invention.

The removal of the pyridine-N-oxide oxygen can even be carried out underthe conditions of the nitration in acetic anhydride as a reactionmedium, otherwise it can be removed according to the literatureconditions (Houben-Weyl, Methoden der org. Chemie [Methods of OrganicChemistry], G. Thieme Verlag, Stuttgart, Vol. 10/2 p. 714 (4th edition))by passing in nitrogen monoxide or by heating at 70° to 80° C. for onehour with phosphorus(III) chloride. A general survey of the preparationof pyridine-N-oxides is also taken from the same place.

The abovementioned process for preparing pyridinecarboxylic acid estersof the formulae Va-c ##STR15## where R² to R⁴ have the abovementionedmeanings, at least one of the radicals being nitro and R⁵ being anydesired substituted alkyl radical, consists in the treatment of apyridinedicarboxylic acid ester or its N-oxide of the formulae Va'-Vc'##STR16## where R² to R⁵ have the abovementioned meanings, at least oneof the radicals R² to R⁴ (namely that (those) which is (are) replaced bynitro) being hydrogen, with nitrating agents and, if appropriate,deoxygenation.

The process is carried out in the same manner as the reaction of thepyridine derivatives Ib described above.

The abovementioned conversions then follow to give the pyridinederivatives Ia. ##STR17##

In comparison with the prior art, the novel nitro-substitutedpyridine-2,3-dicarboxylic anhydrides, esters and imides are accessiblein high yields in a particularly simple manner. Nitro-substitutedpyridine-2,3-dicarboxylic anhydrides and imides were previously unknown.

In the diester series, the 6-methyl-5-nitro, the 6-chloro-5-nitro andthe 6-amino-5-nitro derivative are known.

They all have to be synthesized in an involved reaction based onethoxymethyleneoxalacetic ester and a nitroketone component. In the caseof nitroacetone the yield is only 18% (EP-A 227 932); moreover,nitroacetone cannot be stored and can spontaneously decompose (BeilsteinHI, 661).

In the case of the nitration of 5-chloro-6-hydroxynicotinic acid, thecarboxylic acid radical is removed and replaced by a nitro group(EP-A-467 308). Against the background of the teaching found from theprior art, the nitrations according to the invention were therefore notto be expected. It is also surprising that when using the unsubstitutedN-oxides nitration does not take place in the 4-position, but in the5-position. According to Houben-Weyl, Methoden der org. Chemie [Methodsof Organic Chemistry], G. Thieme Verlag Stuttgart, Vol. 10/1 p. 713 (4thedition), a substitution in the 4- or 6-position would have beenexpected here.

In the context of the preparation of the compounds according to theinvention, it has furthermore been found that amino-substituted pyridinederivatives of the formula Ic ##STR18## where R² to R⁴ have theabovementioned meanings, at least one of the radicals being amino, areobtained when pyridine derivatives of the formula Ia are subjected toreduction.

It has furthermore been found that pyridine derivatives of the formulaIIc ##STR19## where R² to R⁴ have the abovementioned meanings, at leastone of the radicals being amino, are obtained when pyridine derivativesof the formula IIa are subjected to reduction.

Instead of at the stage of the pyridinedicarboxylic anhydrides IIa, thereduction can also be carried out at the corresponding diester stageVa-Vc. These can then be converted to the anhydrides IIc by hydrolysisto the carboxylic acid salts and cyclization (if appropriate using anamine protective group) or reacted directly with the amine III to givecarboxylic ester hemiamides VI which, after hydrolysis to IV, can becyclized to give the compounds Ic according to the invention (ifappropriate using an amine protective group).

A process for preparing compounds Ic, where at least one of the radicalsR² to R⁴ is amino, consists in the reduction of a pyridine derivativeIa. ##STR20##

The reduction can be carried out catalytically on all customarycatalysts with or without pressure in a continuous or discontinuousmanner using hydrogen or hydrazine hydrate as the hydrogen source.Suitable catalysts are, for example, Pt, Pd, Re, Ni, Pd and Ru ormixtures, e.g. Ra/Ni, Pt/Ru oxides. Other catalysts are mentioned inHouben-Weyl, Methoden der org. Chemie. [Methods of Organic Chemistry],G. Thieme Verlag, Stuttgart, Vol. 4/1c pp. 506-537 (4th edition), aswell as promoters and accelerators for accelerating the hydrogenation.Reaction conditions, choice of the solvent, transfer conditions, detailsof selective hydrogenation in the presence of, for example, halogens anddetails of working up are found in the same place, and also in Vol. 11/1pp. 360-381. The latter also describes the reduction with iron (p. 394)with hydrogen sulfide, sulfides and polysulfides (p. 409), and also tinand tin(II) chloride (p. 422), sodium dithionite (p. 437), iron(II)hydroxide (p. 443), lithium aluminum hydride (p. 447), sulfites (p.457), zinc (p. 463), aluminum (p. 469) or an electrolytic reduction.

A process for preparing pyridine derivatives of the formula IIc where atleast one of the radicals R² to R⁴ from the abovementioned meanings isamino, consists in the reduction of a pyridine derivative IIa. ##STR21##

The reduction is carried out in the same manner as the reduction of thepyridine derivatives Ia described above.

A process for preparing pyridine derivatives of the formula Vd where atleast one of the radicals R² to R⁴ from the abovementioned meanings isamino, consists in the reduction of a pyridine derivative Va-Vc.##STR22##

The reduction is carried out in the same manner as the reduction of thepyridine derivatives Ia described above.

A further process for preparing pyridine derivatives of the formula Vewhere at least one of the radicals R² to R⁴ is NR^(6') R^(7'), R^(6')and R^(7') independently of one another being hydrogen or C₁ -C₄ -alkyl,and R^(6') additionally being benzyl or C₁ -C₄ -alkoxy, consists in thereaction of a pyridine derivative Vf with an amine. ##STR23##

For this purpose, the pyridine derivative Vf is initially introduced inone of the abovementioned inert solvents and the amine, as a gas orliquid, and an auxiliary base are added.

In general, the reaction is carried out at from -20° to 250° C.,preferably from 0° to 200° C., particularly preferably from 20° to 180°C.

The molar ratios in which the starting compounds required are reactedwith one another are from 0.9:1 to 3.0:1, preferably from 1.1:1 to1.5:1, for the ratio of amine to pyridine derivative Vf. Theconcentration of the starting materials in the solvent is from 0.1 to 5mol/l, preferably from 0.3 to 2 mol/l.

If only approximately stoichiometric amounts of the amine are employed,expediently from 0.9 to 1.1 equivalents of an organic auxiliary base,based on the starting substance Vf, must be added. Suitable auxiliarybases are organic bases such as trimethylamine, triethylamine,N-ethyldiisopropylamine, triisopropylamine, N,N-dimethylaniline,N,N-dimethylcyclohexylamine, N-methylpyrrolidone, pyridine, quinoline,α,β,γ-picoline, 2,4- and 2,6-lutidine and triethylenediamine.

In the context of the preparation of the compounds according to theinvention, it has furthermore been found that amino-substituted pyridinederivatives of the formula Ic ##STR24## where R² to R⁴ have theabovementioned meaning, at least one of the radicals being amino, areobtained when pyridine derivatives of the formula Id where R² to R⁴ havethe abovementioned meanings, at least one of the radicals being halogen,are reacted with a metal cyanate and the isocyanate formed is hydrolyzedin situ. ##STR25##

For this purpose, the pyridine derivative Id is initially introduced inone of the abovementioned solvents, expediently with addition of atleast 1 to 6 equivalents, preferably 2 to 3 equivalents, of water, themetal cyanate is added and the reaction is then carried out.

In general, the reaction is carried out at from 20° to 200° C.,preferably from 80° to 150° C., particularly preferably from 100° to130° C.

The molar ratios in which the pyridine derivative Id and the metalcyanate are reacted with one another are from 1:0.9 to 1:3, preferablyfrom 1:1.5 to 1:2.5. The concentration of the starting materials in thesolvent is from 0.1 to 5 mol/l, preferably from 0.3 to 2 mol/l.

Suitable cyanates are the salts derived from alkali metals and alkalineearth metals and also iron, cobalt, nickel, copper and zinc, and alsoammonium cyanate.

For working up, the reaction mixture is extracted with water to removethe salts and dried, and the organic phase is purified, e.g. bychromatography or distillation. The reaction products, however, areusually sufficiently pure, so that it is only necessary to filter offfrom the precipitated salt and to concentrate the organic phase.

In comparison to the prior art, the novel amino-substitutedpyridine-2,3-dicarboxylic anhydrides, esters and imides are accessiblein high yields in a particularly simple manner. Amino-substitutedpyridine-2,3-dicarboxylic anhydrides were hitherto unknown. In the imideseries, 6-amino-5-cyano-4-phenylpyridine-2,3-dicarboxyimide was accessedvia a photooxygenation and ring closure reaction (Synth. Commun. 22,2053). Of the esters, dimethyl 4-aminopyridine-2,3-dicarboxylate wasknown by esterification of the corresponding acid, which was isolatedfrom a poisonous fungus [CA. 111, 112 292]. Diethyl5,6-diaminopyridine-2,3-dicarboxylate was prepared by reduction of ananalogous 5-nitro ester, this being carried out with an excess of 261mol % of palladium in the presence of hydrogen (EP-A 227 932). Diethyl6-amino-5-nitropyridine-2,3-dicarboxylate was obtained by nucleophilicdisplacement of a corresponding 6-chloro derivative with ammonia, nodetails of the yield being given (EP-A 227 932). Dimethyl and diethyl5-amino-6-methylpyridine-2,3-dicarboxylates were obtained in an involvedmanner by esterification and Hofmann degradation of a poorly accessiblepyridinetricarboxamide derivative (Beilstein 4-22-006875).

All processes are complicated multistage reactions or requireuneconomical amounts of catalyst.

With respect to the intended use of the compounds I, examples ofsuitable substituents are the following radicals:

R¹ hydrogen;

C₁ -C₄ -alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy,1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particularmethoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy;

C₁ -C₆ -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, in particular propyl,1-methylethyl and 1,1-dimethylethyl, the radicals mentioned being ableto carry one to three of the following groups: C₁ -C₄ -alkoxy asmentioned above, in particular methoxy and ethoxy;

C₁ -C₄ -haloalkoxy such as difluoromethoxy, trifluoromethoxy,chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy,2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy andpentafluoroethoxy, in particular trifluoromethoxy and pentafluoroethoxy;

C₁ -C₄ -alkylthio such as methylthio, ethylthio, propylthio,1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthioand 1,1-dimethylethylthio, in particular methylthio and ethylthio;

C₁ -C₄ -haloalkylthio such as difluoromethylthio, trifluoromethylthio,chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio,2,2-difluoroethylthio, 2,2,2-trifluoroethylthio,2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,2,2,2-trichloroethylthio and pentafluoroethylthio, in particulartrifluoromethylthio and pentafluoroethylthio;

(C₁ -C₄ -dialkyl)amino such as dimethylamino, diethylamino,dipropylamino, diisopropylamino, dibutylamino, methylethylamino, inparticular dimethylamino and methylethylamino;

C₃ -C₈ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl and cyclooctyl, in particular cyclopropyl,cyclopentyl and cyclohexyl;

halogen such as fluorine, chlorine, bromine, iodine, in particularfluorine and chlorine;

additionally C₃ -C₈ -cycloalkyl as mentioned above, in particularcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, which can carry oneto three of the following groups: C₁ -C₆ -alkyl as mentioned above, inparticular methyl, ethyl and isopropyl; haloalkyl as mentioned above forthe homologous haloalkylthio radicals, in particular trifluoromethyl; C₁-C₄ -alkoxy as mentioned above, in particular methoxy and ethoxy; C₁ -C₄-haloalkoxy as mentioned above, in particular trifluoromethoxy; halogenas mentioned above, in particular fluorine and chlorine;

C₃ -C₆ -alkenyl such as 2-propenyl, 2-methylethenyl, 2-butenyl,3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl,1-ethyl-2-propenyl, 1-, 2-, 3-, 4- or 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-pentenyl andethyl-2-methyl-2-pentenyl, in particular ethenyl, 2-propenyl,1-methylethenyl, 2-butenyl, 3-butenyl, 1-methylpropyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, which can be mono- totrisubstituted by halogen, in particular fluorine and chlorine;

additionally C₃ -C₆ -alkynyl such as propargyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl,3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl,4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl,1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, inparticular 1-methyl-2-propynyl and 1,1-dimethyl-2-propynyl, which can bemono- to trisubstituted by halogen as mentioned above, in particularfluorine and chlorine, and/or monosubstituted by phenyl;

R², R³ and R⁴

at least one of the radicals is nitro, an OR⁵ or NR⁶ R⁷ group and theother radicals are:

hydrogen, halogen as mentioned under R¹, in particular fluorine andchlorine; cyano; C₁ -C₆ -alkyl as mentioned under R¹, in particularmethyl, ethyl, propyl, 1-methylethyl and 1,1-dimethylethyl, which cancarry one to five halogen atoms, as mentioned under R¹, in particularfluorine and chlorine, and/or one or two of the following radicals: C₁-C₄ -alkoxy as mentioned under R¹, in particular methoxy, ethoxy,1-methylethoxy and 1,1-dimethylethoxy; C₁ -C₄ -haloalkoxy as mentionedunder R¹, in particular halomethoxy such as difluoromethoxy andtrifluoromethoxy; C₁ -C₄ -alkylthio as mentioned under R¹, in particularmethylthio and ethylthio; C₁ -C₄ -haloalkylthio, as mentioned under R¹,in particular difluoromethylthio and trifluoromethylthio; C₃ -C₆-cycloalkyl as mentioned under R¹, in particular cyclopropyl;

additionally benzyl, which can be mono- to trisubstituted by C₁ -C₄-alkyl as mentioned under R¹, in particular methyl, ethyl and1-methylethyl; C₁ -C₄ -haloalkyl as mentioned under R¹, in particulartrifluoromethyl and chlorodifluoromethyl; C₁ -C₄ -alkoxy as mentionedunder R¹, in particular methoxy and ethoxy; C₁ -C₄ -haloalkoxy asmentioned under R¹, in particular trifluoromethoxy, trichloromethoxy andpentafluoroethoxy; C₁ -C₄ -alkylthio as mentioned under R¹, inparticular methylthio and ethylthio; C₁ -C₄ -haloalkylthio as mentionedunder R¹, in particular difluoromethylthio, trifluoromethylthio andpentafluoromethylthio; halogen, in particular fluorine and chlorine;cyano or nitro;

additionally C₃ -C₈ -cycloalkyl, as mentioned under R¹, in particularcyclopropyl, cyclopentyl and cyclohexyl; which can be mono- totrisubstituted by C₁ -C₄ -alkyl as mentioned under R¹, in particularmethyl and ethyl; or halogen as mentioned under R¹, in particularfluorine and chlorine;

C₂ -C₆ -alkenyl as mentioned under R¹, additionally 1-ethenyl,1-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 1-ethyl-1-propenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1,2-dimethyl-1-butenyl, 1,3-dimethyl-1-butenyl,2,3-dimethyl-1-butenyl, 3,3-dimethyl-1-butenyl, ethyl-1-butenyl,2-ethyl-1-butenyl, 1-ethyl-2-methyl-1-pentenyl, in particular ethenyl,1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methylpropenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl,2-methyl-2-propenyl, which can be mono- to trisubstituted by halogen asmentioned under R¹, in particular fluorine and chlorine; or C₁ -C₃-alkoxy as mentioned under R¹, in particular methoxy and ethoxy; and/ormonosubstituted by phenyl, the phenyl radical in turn being able tocarry one to three of the following groups: alkyl as mentioned under R¹,in particular methyl, ethyl and 1-methylethyl; haloalkyl as mentionedunder R¹, in particular trifluoromethyl and chlorodifluoromethyl; alkoxyas mentioned under R¹, in particular methoxy and ethoxy; haloalkoxy asmentioned under R¹, in particular trifluoromethoxy, trichloromethoxy andpentafluoroethoxy; alkylthio as mentioned under R¹, in particularmethylthio and ethylthio; haloalkylthio as mentioned under R¹, inparticular difluoromethylthio, trifluoromethylthio andpentafluoromethylthio; halogen as mentioned under R¹, in particularfluorine and chlorine; cyano or nitro;

C₂ -C₆ -alkynyl, as mentioned under R¹, in addition ethynyl, 1-propynyl,1-butynyl, 1-pentynyl, 1-hexynyl, 3-methyl-1-pentynyl,4-methyl-1-pentynyl, in particular ethynyl, 1-propynyl and propargyl,which can be mono- to trisubstituted by halogen as mentioned above, inparticular fluorine and chlorine; or alkoxy as mentioned above, inparticular methoxy and ethoxy; and/or monosubstituted by phenyl, thephenyl radical in turn being able to carry one to three of the followinggroups: alkyl as mentioned above, in particular methyl, ethyl and1-methylethyl; haloalkyl as mentioned above, in particulartrifluoromethyl and chlorodifluoromethyl; alkoxy as mentioned above, inparticular methoxy and ethoxy; haloalkoxy as mentioned above, inparticular trifluoromethoxy, trichloromethoxy and pentafluoroethoxy;alkylthio as mentioned above, in particular methylthio and ethylthio;haloalkylthio as mentioned above, in particular difluoromethylthio,trifluoromethylthio and pentafluoromethylthio; halogen as mentionedabove, in particular fluorine and chlorine; cyano or nitro;

additionally C₁ -C₄ -alkoxy or -alkylthio as mentioned under R¹, inparticular methoxy and ethoxy, methylthio and ethylthio;

C₁ -C₄ -haloalkoxy or -haloalkylthio as mentioned above, in particulartrifluoromethoxy, trichloromethoxy and pentafluoroethoxy,difluoromethylthio, trifluoromethylthio and pentafluoroethylthio;

C₂ -C₅ -alkenyloxy such as vinyloxy, 2-propenyloxy, 1-methylethenyloxy,2-methyl-3-butenyloxy, in particular 2-propenyloxy and2-methyl-3-butenyloxy;

C₂ -C₅ -alkynyloxy such as ethynyloxy, 2-propynyloxy,1-methylethynyloxy, 2-methyl-3-butynyloxy, in particular 2-propynyloxyand 2-methyl-3-butynyloxy;

C₁ -C₄ -alkylsulfinyl such as methylsulfinyl, ethylsulfinyl,n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, tert-butylsulfinyl,in particular methylsulfinyl;

C₁ -C₄ -alkylsulfonyl such as methylsulfonyl, ethylsulfonyl,n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, tert-butylsulfonyl,in particular methylsulfonyl;

C₁ -C₄ -haloalkylsulfonyl such as trifluoromethylsulfonyl,pentafluoroethylsulfonyl, monofluorobutylsulfonyl, in particulartrifluoromethylsulfonyl; phenoxy or phenylthio, which can be mono- totrisubstituted by C₁ -C₄ -alkyl as mentioned under R¹, in particularmethyl, ethyl and isopropyl; haloalkyl as mentioned under R¹, inparticular trifluoromethyl and chlorodifluoromethyl; alkoxy as mentionedabove, in particular methoxy and ethoxy; haloalkoxy as mentioned above,in particular trifluoromethoxy, trichloromethoxy and pentafluoroethoxy;alkylthio as mentioned above, in particular methylthio and ethylthio;haloalkylthio as mentioned above, in particular difluoromethylthio,trifluoromethylthio and pentafluoromethylthio; halogen as mentionedabove, in particular fluorine and chlorine; cyano or nitro;

a 5- or 6-membered saturated or aromatic heterocyclic radical,containing one or two heteroatoms selected from the group consisting ofoxygen, sulfur and nitrogen, such as tetrahydrofuryl, tetrahydropyranyl,furyl, thienyl, thiazolyl, pyrazolyl, pyrrolyl, pyridyl, morpholino,piperidino, pyrimidyl, for example 2-tetrahydrofuranyl,3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl,3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl,5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl,4-imidazolyl, 5-imidazolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl,4-pyrazolyl, 5-pyrazolyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, which cancarry one to three of the following substituents: C₁ -C₃ -alkyl asmentioned above, in particular methyl and ethyl, halogen as mentionedabove, in particular fluorine and chlorine, C₁ -C₃ -alkoxy as mentionedunder R¹, in particular methoxy and ethoxy; or C₁ -C₄ -alkoxycarbonylsuch as methoxycarbonyl and ethoxycarbonyl, in particularmethoxycarbonyl;

phenyl, which can carry one to three of the following groups: C₁ -C₆-alkyl as mentioned under R¹, in particular methyl, ethyl and isopropyl;C₁ -C₆ -haloalkyl as mentioned under R¹, in particular trifluoromethyland chlorodifluoromethyl; C₁ -C₆ -alkoxy as mentioned under R¹, inparticular methoxy and ethoxy; C₁ -C₆ -haloalkoxy as mentioned under R¹,in particular trifluoromethoxy, trichloromethoxy and pentafluoroethoxy;C₁ -C₆ -alkylthio as mentioned under R¹, in particular methylthio andethylthio; C₁ -C₆ -haloalkylthio as mentioned under R¹, in particulardifluoromethylthio, trifluoromethylthio and pentafluoromethylthio;halogen as mentioned under R¹, in particular fluorine and chlorine;cyano or nitro;

R⁵ hydrogen, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -haloalkylcarbonyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkoxy-C₂ -C₄ -alkoxycarbonyl, C₁ -C₄-alkylcarbamoyl, C₁ -C₄ -dialkylcarbamoyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄-haloalkylsulfonyl, sulfamoyl, C₁ -C₄ -alkylaminosulfonyl, C₁ -C₄-dialkylaminosulfonyl, phenylsulfonyl, which can be mono- totrisubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkoxy, C₁ -C₄ -alkylthio, halogen, cyano or nitro, the alkyl,alkyloxy, haloalkyl, alkylthio and alkylamino constituents in theindividual radicals contained in the definitions corresponding to thoseindicated above in the individual definitions listed;

R⁶ hydrogen, C₁ -C₄ -alkyl, in particular methyl and ethyl, benzyl, C₁-C₄ -alkoxy, e.g. methoxy and ethoxy, or together with R⁷ C═S;

R⁷ C₁ -C₄ -alkyl, in particular methyl and ethyl, and the radicalslisted for R⁵.

Examples of preferred radical combinations in the pyridine ring can betaken from the table below, R.sup. corresponding to a radical from thegroup L1 to L66, in particular to a 1-(cyclopropyl)ethyl radical or acyclopropyl radical.

    ______________________________________                                         ##STR26##                                                                    R.sup.2    R.sup.3        R.sup.4                                             ______________________________________                                        NO.sub.2   H              H                                                   NO.sub.2   F              H                                                   NO.sub.2   H              F                                                   NO.sub.2   F              F                                                   NO.sub.2   Cl             H                                                   NO.sub.2   H              Cl                                                  NO.sub.2   Cl             Cl                                                  NO.sub.2   F              Cl                                                  NO.sub.2   Cl             F                                                   NO.sub.2   CN             H                                                   NO.sub.2   H              CN                                                  NO.sub.2   CN             CN                                                  NO.sub.2   CN             F                                                   NO.sub.2   F              CN                                                  NO.sub.2   Cl             CN                                                  NO.sub.2   CN             Cl                                                  NO.sub.2   CH.sub.3       H                                                   NO.sub.2   H              CH.sub.3                                            NO.sub.2   CH.sub.3       CH.sub.3                                            NO.sub.2   F              CH.sub.3                                            NO.sub.2   CH.sub.3       F                                                   NO.sub.2   CH.sub.3       Cl                                                  NO.sub.2   Cl             CH.sub.3                                            NO.sub.2   C.sub.2 H.sub.5                                                                              F                                                   NO.sub.2   F              C.sub.2 H.sub.5                                     NO.sub.2   CF.sub.3       H                                                   NO.sub.2   H              CF.sub.3                                            NO.sub.2   Cl             CF.sub.3                                            NO.sub.2   CF.sub.3       Cl                                                  NO.sub.2   C.sub.2 F.sub.5                                                                              H                                                   NO.sub.2   H              C.sub.2 F.sub.5                                     NO.sub.2   CH.sub.2 OCH.sub.3                                                                           H                                                   NO.sub.2   H              CH.sub.2 OCH.sub.3                                  NO.sub.2   CH.sub.2 OCH.sub.3                                                                           F                                                   NO.sub.2   CH.sub.2 SCH.sub.3                                                                           H                                                   NO.sub.2   H              CH.sub.2 SCH.sub.3                                  NO.sub.2   CH.sub.2 SCH.sub.3                                                                           Cl                                                  NO.sub.2   Cl             CH.sub.2 SCH.sub.3                                  NO.sub.2   CH.sub.2 -cyclopropyl                                                                        H                                                   NO.sub.2   1-(cyclopropyl)ethyl                                                                         H                                                   NO.sub.2   CH.sub.2 CN    H                                                   NO.sub.2   H              CH.sub.2 CN                                         NO.sub.2   CH.sub.3       CH.sub.2 CN                                         NO.sub.2   benzyl         H                                                   NO.sub.2   Cl             benzyl                                              NO.sub.2   benzyl         F                                                   NO.sub.2   F              benzyl                                              NO.sub.2   4-chlorobenzyl H                                                   NO.sub.2   3-CF.sub.3 -benzyl                                                                           H                                                   NO.sub.2   2,4-Cl.sub.2 -benzyl                                                                         H                                                   NO.sub.2   3-OCH.sub.3 -phenyl                                                                          H                                                   NO.sub.2   H              3-OCH.sub.3 -benzyl                                 NO.sub.2   3-CN-benzyl    H                                                   NO.sub.2   cyclopropyl    H                                                   NO.sub.2   cyclopropyl    Cl                                                  NO.sub.2   cyclopropyl    F                                                   NO.sub.2   CHCH.sub.2     H                                                   NO.sub.2   F              CHCH.sub.2                                          NO.sub.2   CFCF.sub.2     H                                                   NO.sub.2   CH.sub.3       CFCF.sub.2                                          NO.sub.2   CH.sub.3       benzyl                                              NO.sub.2   CHCHOCH.sub.3  H                                                   NO.sub.2   CHCHOCH.sub.3  Cl                                                  NO.sub.2   CHCHOCH.sub.3  F                                                   NO.sub.2   CHCH-phenyl    H                                                   NO.sub.2   CHCH-phenyl    F                                                   NO.sub.2   CHCH-phenyl    Cl                                                  NO.sub.2   CHCH-(3-chloro-                                                                              H                                                              phenyl)                                                            NO.sub.2   CHCH-(3-chloro-                                                                              F                                                              phenyl)                                                            NO.sub.2                                                                                  ##STR27##     H                                                   NO.sub.2                                                                                  ##STR28##     H                                                   NO.sub.2                                                                                  ##STR29##     F                                                   NO.sub.2   CH.sub.3 O     H                                                   NO.sub.2   CH.sub.3 O     F                                                   NO.sub.2   CH.sub.3 O     Cl                                                  NO.sub.2   CH.sub.3 O     CH.sub.3                                            NO.sub.2   H              CH.sub.3 O                                          NO.sub.2   Cl             CH.sub.3 O                                          NO.sub.2   F              CH.sub.3 O                                          NO.sub.2   CH.sub.3       CH.sub.3 O                                          NO.sub.2   CH.sub.3 O     CH.sub.3 O                                          NO.sub.2   CH.sub.3 S     H                                                   NO.sub.2   CH.sub.3 S     F                                                   NO.sub.2   CH.sub.3 S     Cl                                                  NO.sub.2   CH.sub.3 S     CH.sub.3                                            NO.sub.2   H              CH.sub.3 S                                          NO.sub.2   F              CH.sub.3 S                                          NO.sub.2   Cl             CH.sub.3 S                                          NO.sub.2   CH.sub.3       CH.sub.3 S                                          NO.sub.2   CF.sub.3 O     H                                                   NO.sub.2   CF.sub.3 O     F                                                   NO.sub.2   CF.sub.3 O     Cl                                                  NO.sub.2   F.sub.2 CHO    H                                                   NO.sub.2   F.sub.2 CHO    F                                                   NO.sub.2   F.sub.2 CHO    Cl                                                  NO.sub.2   SCF.sub.3      H                                                   NO.sub.2   SCF.sub.3      F                                                   NO.sub.2   SCF.sub.3      Cl                                                  NO.sub.2   CH.sub.3 SO    H                                                   NO.sub.2   CH.sub.3 SO    F                                                   NO.sub.2   CH.sub.3 SO    Cl                                                  NO.sub.2   CH.sub.3 SO.sub.2                                                                            H                                                   NO.sub.2   CH.sub.3 SO.sub.2                                                                            Cl                                                  NO.sub.2   CH.sub.3 SO.sub.2                                                                            F                                                   NO.sub.2   CF.sub.3 SO.sub.2                                                                            H                                                   NO.sub.2   CF.sub.3 SO.sub.2                                                                            F                                                   NO.sub.2   CF.sub.3 SO.sub.2                                                                            Cl                                                  NO.sub.2   O-phenyl       H                                                   NO.sub.2   O-phenyl       F                                                   NO.sub.2   O-(4-Cl-phenyl)                                                                              H                                                   NO.sub.2   O-(3-CF.sub.3 -phenyl)                                                                       H                                                   NO.sub.2   O-(2,4-Cl.sub.2 -phenyl)                                                                     H                                                   NO.sub.2   O-(4-CH.sub.3 O-phenyl)                                                                      H                                                   NO.sub.2   O-(3-CN-phenyl)                                                                              H                                                   NO.sub.2   S-phenyl       H                                                   NO.sub.2   S-(3-Cl-phenyl)                                                                              H                                                   NO.sub.2   2-tetrahydrofuranyl                                                                          H                                                   NO.sub.2   3-tetrahydrofuranyl                                                                          H                                                   NO.sub.2   2-tetrahydrothienyl                                                                          H                                                   NO.sub.2   3-tetrahydrothienyl                                                                          H                                                   NO.sub.2   2-tetrahydropyranyl                                                                          H                                                   NO.sub.2   3-tetrahydropyranyl                                                                          H                                                   NO.sub.2   4-tetrahydropyranyl                                                                          H                                                   NO.sub.2   2-furyl        H                                                   NO.sub.2   3-furyl        H                                                   NO.sub.2   2-thienyl      H                                                   NO.sub.2   3-thienyl      H                                                   NO.sub.2   3-isoxazolyl   H                                                   NO.sub.2   4-isoxazolyl   H                                                   NO.sub.2   5-isoxazolyl   H                                                   NO.sub.2   3-isothiazolyl H                                                   NO.sub.2   4-isothiazolyl H                                                   NO.sub.2   5-isothiazolyl H                                                   NO.sub.2   2-oxazolyl     H                                                   NO.sub.2   4-oxazolyl     H                                                   NO.sub.2   5-oxazolyl     H                                                   NO.sub.2   2-thiazolyl    H                                                   NO.sub.2   4-thiazolyl    H                                                   NO.sub.2   5-thiazolyl    H                                                   NO.sub.2   2-imidazolyl   H                                                   NO.sub.2   4-imidazolyl   H                                                   NO.sub.2   5-imidazolyl   H                                                   NO.sub.2   2-pyrrolyl     H                                                   NO.sub.2   3-pyrrolyl     H                                                   NO.sub.2   3-pyrazolyl    H                                                   NO.sub.2   4-pyrazolyl    H                                                   NO.sub.2   5-pyrazolyl    H                                                   NO.sub.2   2-pyridyl      H                                                   NO.sub.2   3-pyridyl      H                                                   NO.sub.2   4-pyridyl      H                                                   NO.sub.2   phenyl         H                                                   NO.sub.2   4-Cl-phenyl    H                                                   NO.sub.2   2,4-Cl.sub.2 -phenyl                                                                         H                                                   NO.sub.2   3-CF.sub.3 -phenyl                                                                           H                                                   NO.sub.2   3-CH.sub.3 O-phenyl                                                                          H                                                   H          NO.sub.2       H                                                   H          NO.sub.2       F                                                   H          NO.sub.2       Cl                                                  H          NO.sub.2       CN                                                  H          NO.sub.2       CH.sub.3                                            H          NO.sub.2       CH.sub.3 O                                          H          NO.sub.2       C.sub.2 H.sub.5 O                                   H          NO.sub.2       CH.sub.3 S                                          H          NO.sub.2       C.sub.2 H.sub.5 S                                   H          NO.sub.2       benzyl                                              H          NO.sub.2       CFCF.sub.2                                          H          NO.sub.2       C.sub.2 F.sub.5                                     H          NO.sub.2       cyclopropyl                                         H          NO.sub.2       C.sub.2 H.sub.5                                     H          NO.sub.2       CF.sub.3 O                                          H          NO.sub.2       F.sub.2 CHO                                         H          NO.sub.2       C.sub.2 F.sub.5 O                                   H          NO.sub.2       CF.sub.3 S                                          H          NO.sub.2       F.sub.2 CHS                                         H          NO.sub.2       CF.sub.3                                            H          NO.sub.2       CH.sub.3 SO                                         H          NO.sub.2       CH.sub.3 SO.sub.2                                   H          NO.sub.2       CF.sub.3 SO.sub.2                                   H          NO.sub.2       O-phenyl                                            H          NO.sub.2       O-(4-Cl-phenyl)                                     H          NH.sub.2       O-(3-CF.sub.3 -phenyl)                              H          NH.sub.2       H                                                   H          NH.sub.2       F                                                   H          NH.sub.2       Cl                                                  H          NH.sub.2       CN                                                  H          NH.sub.2       CH.sub.3                                            H          NH.sub.2       CH.sub.3 O                                          H          NH.sub.2       C.sub.2 H.sub.5 O                                   H          NH.sub.2       CH.sub.3 S                                          H          NH.sub.2       C.sub.2 H.sub.5 S                                   H          NH.sub.2       benzyl                                              H          NH.sub.2       CFCF.sub.2                                          H          NH.sub.2       C.sub.2 F.sub.5                                     H          NH.sub.2       cyclopropyl                                         H          NH.sub.2       C.sub.2 H.sub.5                                     H          NH.sub.2       CF.sub.3 O                                          H          NH.sub.2       F.sub.2 CHO                                         H          NH.sub.2       C.sub.2 F.sub.5 O                                   H          NH.sub.2       CF.sub.3 S                                          H          NH.sub.2       F.sub.2 CHS                                         H          NH.sub.2       CF.sub.3                                            H          NH.sub.2       CH.sub.3 SO                                         H          NH.sub.2       CH.sub.3 SO.sub.2                                   H          NH.sub.2       CF.sub.3 SO.sub.2                                   H          NH.sub.2       O-phenyl                                            H          NH.sub.2       O-(4-Cl-phenyl)                                     H          CH.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              H          CH.sub.3 (CO)NH                                                                              H                                                   H          CH.sub.3 (CO)NH                                                                              F                                                   H          CH.sub.3 (CO)NH                                                                              Cl                                                  H          CH.sub.3 (CO)NH                                                                              CN                                                  H          CH.sub.3 (CO)NH                                                                              CH.sub.3                                            H          CH.sub.3 (CO)NH                                                                              CH.sub.3 O                                          H          CH.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   H          CH.sub.3 (CO)NH                                                                              CH.sub.3 S                                          H          CH.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   H          CH.sub.3 (CO)NH                                                                              benzyl                                              H          CH.sub.3 (CO)NH                                                                              CFCF.sub.2                                          H          CH.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     H          CH.sub.3 (CO)NH                                                                              cyclopropyl                                         H          CH.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     H          CH.sub.3 (CO)NH                                                                              CF.sub.3 O                                          H          CH.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         H          CH.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   H          CH.sub.3 (CO)NH                                                                              CF.sub.3 S                                          H          CH.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         H          CH.sub.3 (CO)NH                                                                              CF.sub.3                                            H          CH.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         H          CH.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   H          CH.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   H          CH.sub.3 (CO)NH                                                                              O-phenyl                                            H          CH.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     H          CF.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              H          CF.sub.3 (CO)NH                                                                              H                                                   H          CF.sub.3 (CO)NH                                                                              F                                                   H          CF.sub.3 (CO)NH                                                                              Cl                                                  H          CF.sub.3 (CO)NH                                                                              CN                                                  H          CF.sub.3 (CO)NH                                                                              CH.sub.3                                            H          CF.sub.3 (CO)NH                                                                              CH.sub.3 O                                          H          CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   H          CF.sub.3 (CO)NH                                                                              CH.sub.3 S                                          H          CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   H          CF.sub.3 (CO)NH                                                                              benzyl                                              H          CF.sub.3 (CO)NH                                                                              CFCF.sub.2                                          H          CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     H          CF.sub.3 (CO)NH                                                                              cyclopropyl                                         H          CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     H          CF.sub.3 (CO)NH                                                                              CF.sub.3 O                                          H          CF.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         H          CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   H          CF.sub.3 (CO)NH                                                                              CF.sub.3 S                                          H          CF.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         H          CF.sub.3 (CO)NH                                                                              CF.sub.3                                            H          CF.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         H          CF.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   H          CF.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   H          CF.sub.3 (CO)NH                                                                              O-phenyl                                            H          CF.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     H          CH.sub.3 NH    O-(3-CF.sub.3 -phenyl)                              H          CH.sub.3 NH    H                                                   H          CH.sub.3 NH    F                                                   H          CH.sub.3 NH    Cl                                                  H          CH.sub.3 NH    CN                                                  H          CH.sub.3 NH    CH.sub.3                                            H          CH.sub.3 NH    CH.sub.3 O                                          H          CH.sub.3 NH    C.sub.2 H.sub.5 O                                   H          CH.sub.3 NH    CH.sub.3 S                                          H          CH.sub.3 NH    C.sub.2 H.sub.5 S                                   H          CH.sub.3 NH    benzyl                                              H          CH.sub.3 NH    CFCF.sub.2                                          H          CH.sub.3 NH    C.sub.2 F.sub.5                                     H          CH.sub.3 NH    cyclopropyl                                         H          CH.sub.3 NH    C.sub.2 H.sub.5                                     H          CH.sub.3 NH    CF.sub.3 O                                          H          CH.sub.3 NH    F.sub.2 CHO                                         H          CH.sub.3 NH    C.sub.2 F.sub.5 O                                   H          CH.sub.3 NH    CF.sub.3 S                                          H          CH.sub.3 NH    F.sub.2 CHS                                         H          CH.sub.3 NH    CF.sub.3                                            H          CH.sub.3 NH    CH.sub.3 SO                                         H          CH.sub.3 NH    CH.sub.3 SO.sub.2                                   H          CH.sub.3 NH    CF.sub.3 SO.sub.2                                   H          CH.sub.3 NH    O-phenyl                                            H          CH.sub.3 NH    O-(4-Cl-phenyl)                                     H          CH.sub.3 CO.sub.2                                                                            O-(3-CF.sub.3 -phenyl)                              H          CH.sub.3 CO.sub.2                                                                            H                                                   H          CH.sub.3 CO.sub.2                                                                            F                                                   H          CH.sub.3 CO.sub.2                                                                            Cl                                                  H          CH.sub.3 CO.sub.2                                                                            CN                                                  H          CH.sub.3 CO.sub.2                                                                            CH.sub.3                                            H          CH.sub.3 CO.sub.2                                                                            CH.sub.3 O                                          H          CH.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5 O                                   H          CH.sub.3 CO.sub.2                                                                            CH.sub.3 S                                          H          CH.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5 S                                   H          CH.sub.3 CO.sub.2                                                                            benzyl                                              H          CH.sub.3 CO.sub.2                                                                            CFCF.sub.2                                          H          CH.sub.3 CO.sub.2                                                                            C.sub.2 F.sub.5                                     H          CH.sub.3 CO.sub.2                                                                            cyclopropyl                                         H          CH.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5                                     H          CH.sub.3 CO.sub.2                                                                            CF.sub.3 O                                          H          CH.sub.3 CO.sub.2                                                                            F.sub.2 CHO                                         H          CH.sub.3 CO.sub.2                                                                            C.sub.2 F.sub.5 O                                   H          CH.sub.3 CO.sub.2                                                                            CF.sub.3 S                                          H          CH.sub.3 CO.sub.2                                                                            F.sub.2 CHS                                         H          CH.sub.3 CO.sub.2                                                                            CF.sub.3                                            H          CH.sub.3 CO.sub.2                                                                            CH.sub.3 SO                                         H          CH.sub.3 CO.sub.2                                                                            CH.sub.3 SO.sub.2                                   H          CH.sub.3 CO.sub.2                                                                            CF.sub.3 SO.sub.2                                   H          CH.sub.3 CO.sub.2                                                                            O-phenyl                                            H          CH.sub.3 CO.sub.2                                                                            O-(4-Cl-phenyl)                                     H          CF.sub.3 CO.sub.2                                                                            O-(3-CF.sub.3 -phenyl)                              H          CF.sub.3 CO.sub.2                                                                            H                                                   H          CF.sub.3 CO.sub.2                                                                            F                                                   H          CF.sub.3 CO.sub.2                                                                            Cl                                                  H          CF.sub.3 CO.sub.2                                                                            CN                                                  H          CF.sub.3 CO.sub.2                                                                            CH.sub.3                                            H          CF.sub.3 CO.sub.2                                                                            CH.sub.3 O                                          H          CF.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5 O                                   H          CF.sub.3 CO.sub.2                                                                            CH.sub.3 S                                          H          CF.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5 S                                   H          CF.sub.3 CO.sub.2                                                                            benzyl                                              H          CF.sub.3 CO.sub.2                                                                            CFCF.sub.2                                          H          CF.sub.3 CO.sub.2                                                                            C.sub.2 F.sub.5                                     H          CF.sub.3 CO.sub.2                                                                            cyclopropyl                                         H          CF.sub.3 CO.sub.2                                                                            C.sub.2 H.sub.5                                     H          CF.sub.3 CO.sub.2                                                                            CF.sub.3 O                                          H          CF.sub.3 CO.sub.2                                                                            F.sub.2 CHO                                         H          CF.sub.3 CO.sub.2                                                                            C.sub.2 F.sub.5 O                                   H          CF.sub.3 CO.sub.2                                                                            CF.sub.3 S                                          H          CF.sub.3 CO.sub.2                                                                            F.sub.2 CHS                                         H          CF.sub.3 CO.sub.2                                                                            CF.sub.3                                            H          CF.sub.3 CO.sub.2                                                                            CH.sub.3 SO                                         H          CF.sub.3 CO.sub.2                                                                            CH.sub.3 SO.sub.2                                   H          CF.sub.3 CO.sub.2                                                                            CF.sub.3 SO.sub.2                                   H          CF.sub.3 CO.sub.2                                                                            O-phenyl                                            H          CF.sub.3 CO.sub.2                                                                            O-(4-Cl-phenyl)                                     H          CF.sub.3 SO.sub.2                                                                            O-(3-CF.sub.3 -phenyl)                              H          CF.sub.3 SO.sub.2                                                                            H                                                   H          CF.sub.3 SO.sub.2                                                                            F                                                   H          CF.sub.3 SO.sub.2                                                                            Cl                                                  H          CF.sub.3 SO.sub.2                                                                            CN                                                  H          CF.sub.3 SO.sub.2                                                                            CH.sub.3                                            H          CF.sub.3 SO.sub.2                                                                            CH.sub.3 O                                          H          CF.sub.3 SO.sub.2                                                                            C.sub.2 H.sub.5 O                                   H          CF.sub.3 SO.sub.2                                                                            CH.sub.3 S                                          H          CF.sub.3 SO.sub.2                                                                            C.sub.2 H.sub.5 S                                   H          CF.sub.3 SO.sub.2                                                                            benzyl                                              H          CF.sub.3 SO.sub.2                                                                            CFCF.sub.2                                          H          CF.sub.3 SO.sub.2                                                                            C.sub.2 F.sub.5                                     H          CF.sub.3 SO.sub.2                                                                            cyclopropyl                                         H          CF.sub.3 SO.sub.2                                                                            C.sub.2 H.sub.5                                     H          CF.sub.3 SO.sub.2                                                                            CF.sub.3 O                                          H          CF.sub.3 SO.sub.2                                                                            F.sub.2 CHO                                         H          CF.sub.3 SO.sub.2                                                                            C.sub.2 F.sub.5 O                                   H          CF.sub.3 SO.sub.2                                                                            CF.sub.3 S                                          H          CF.sub.3 SO.sub.2                                                                            F.sub.2 CHS                                         H          CF.sub.3 SO.sub.2                                                                            CF.sub.3                                            H          CF.sub.3 SO.sub.2                                                                            CH.sub.3 SO                                         H          CF.sub.3 SO.sub.2                                                                            CH.sub.3 SO.sub.2                                   H          CF.sub.3 SO.sub.2                                                                            CF.sub.3 SO.sub.2                                   H          CF.sub.3 SO.sub.2                                                                            O-phenyl                                            H          CF.sub.3 SO.sub.2                                                                            O-(4-Cl-phenyl)                                     F          NO.sub.2       CH.sub.3                                            F          NO.sub.2       CF.sub.3 O                                          F          NO.sub.2       F.sub.2 CHO                                         F          NO.sub.2       C.sub.2 F.sub.5 O                                   F          NO.sub.2       CF.sub.3 S                                          F          NO.sub.2       F.sub.2 CHS                                         F          NO.sub.2       CH.sub.3 SO                                         F          NO.sub.2       CH.sub.3 SO.sub.2                                   F          NO.sub.2       CF.sub.3 SO.sub.2                                   F          NO.sub.2       O-phenyl                                            F          NO.sub.2       O-(4-Cl-phenyl)                                     F          NO.sub.2       ClCF.sub.2 O                                        F          NO.sub.2       i-C.sub.3 H.sub.7                                   F          NO.sub.2       i-C.sub.4 H.sub.9                                   Cl         NO.sub.2       O-(3-CF.sub.3 -phenyl)                              Cl         NO.sub.2       H                                                   Cl         NO.sub.2       F                                                   Cl         NO.sub.2       Cl                                                  Cl         NO.sub.2       CN                                                  Cl         NO.sub.2       CH.sub.3                                            Cl         NO.sub.2       CH.sub.3 O                                          Cl         NO.sub.2       C.sub.2 H.sub.5 O                                   Cl         NO.sub.2       CH.sub.3 S                                          Cl         NO.sub.2       C.sub.2 H.sub.5 S                                   Cl         NO.sub.2       benzyl                                              Cl         NO.sub.2       CFCF.sub.2                                          Cl         NO.sub.2       C.sub.2 F.sub.5                                     Cl         NO.sub.2       cyclopropyl                                         Cl         NO.sub.2       C.sub.2 H.sub.5                                     Cl         NO.sub.2       CF.sub.3 O                                          Cl         NO.sub.2       F.sub.2 CHO                                         Cl         NO.sub.2       C.sub.2 F.sub.5 O                                   Cl         NO.sub.2       CF.sub.3 S                                          Cl         NO.sub.2       F.sub.2 CHS                                         Cl         NO.sub.2       CF.sub.3                                            Cl         NO.sub.2       CH.sub.3 SO                                         Cl         NO.sub.2       CH.sub.3 SO.sub.2                                   Cl         NO.sub.2       CF.sub.3 SO.sub.2                                   Cl         NO.sub.2       O-phenyl                                            Cl         NO.sub.2       O-(4-Cl-phenyl)                                     CH.sub.3 O NO.sub.2       O-(3-CF.sub.3 -phenyl)                              CH.sub.3 O NO.sub.2       H                                                   CH.sub.3 O NO.sub.2       F                                                   CH.sub.3 O NO.sub.2       Cl                                                  CH.sub.3 O NO.sub.2       CN                                                  CH.sub.3 O NO.sub.2       CH.sub.3                                            CH.sub.3 O NO.sub.2       CH.sub.3 O                                          CH.sub.3 O NO.sub.2       C.sub.2 H.sub.5 O                                   CH.sub.3 O NO.sub.2       CH.sub.3 S                                          CH.sub.3 O NO.sub.2       C.sub.2 H.sub.5 S                                   CH.sub.3 O NO.sub.2       benzyl                                              CH.sub.3 O NO.sub.2       CFCF.sub.2                                          CH.sub.3 O NO.sub.2       C.sub.2 F.sub.5                                     CH.sub.3 O NO.sub.2       cyclopropyl                                         CH.sub.3 O NO.sub.2       C.sub.2 H.sub.5                                     CH.sub.3 O NO.sub.2       CF.sub.3 O                                          CH.sub.3 O NO.sub.2       F.sub.2 CHO                                         CH.sub.3 O NO.sub.2       C.sub.2 F.sub.5 O                                   CH.sub.3 O NO.sub.2       CF.sub.3 S                                          CH.sub.3 O NO.sub.2       F.sub.2 CHS                                         CH.sub.3 O NO.sub.2       CF.sub.3                                            CH.sub.3 O NO.sub.2       CH.sub.3 SO                                         CH.sub.3 O NO.sub.2       CH.sub.3 SO.sub.2                                   CH.sub.3 O NO.sub.2       CF.sub.3 SO.sub.2                                   CH.sub.3 O NO.sub.2       O-phenyl                                            CH.sub.3 O NO.sub.2       O-(4-Cl-phenyl)                                     CH.sub.3   NO.sub.2       O-(3-CF.sub.3 -phenyl)                              CH.sub.3   NO.sub.2       H                                                   CH.sub.3   NO.sub.2       F                                                   CH.sub.3   NO.sub.2       Cl                                                  CH.sub.3   NO.sub.2       CN                                                  CH.sub.3   NO.sub.2       CH.sub.3                                            CH.sub.3   NO.sub.2       CH.sub.3 O                                          CH.sub.3   NO.sub.2       C.sub.2 H.sub.5 O                                   CH.sub.3   NO.sub.2       CH.sub.3 S                                          CH.sub.3   NO.sub.2       C.sub.2 H.sub.5 S                                   CH.sub.3   NO.sub.2       benzyl                                              CH.sub.3   NO.sub.2       CFCF.sub.2                                          CH.sub.3   NO.sub.2       C.sub.2 F.sub.5                                     CH.sub.3   NO.sub.2       cyclopropyl                                         CH.sub.3   NO.sub.2       C.sub.2 H.sub.5                                     CH.sub.3   NO.sub.2       CF.sub.3 O                                          CH.sub.3   NO.sub.2       F.sub.2 CHO                                         CH.sub.3   NO.sub.2       C.sub.2 F.sub.5 O                                   CH.sub.3   NO.sub.2       CF.sub.3 S                                          CH.sub.3   NO.sub.2       F.sub.2 CHS                                         CH.sub.3   NO.sub.2       CF.sub.3                                            CH.sub.3   NO.sub.2       CH.sub.3 SO                                         CH.sub.3   NO.sub.2       CH.sub.3 SO.sub.2                                   CH.sub.3   NO.sub.2       CF.sub.3 SO.sub.2                                   CH.sub.3   NO.sub.2       O-phenyl                                            CH.sub.3   NO.sub.2       O-(4-Cl-phenyl)                                     F          NH.sub.2       C.sub.2 H.sub.5                                     F          NH.sub.2       CF.sub.3 O                                          F          NH.sub.2       F.sub.2 CHO                                         F          NH.sub.2       C.sub.2 H.sub.5 O                                   F          NH.sub.2       CF.sub.3 S                                          F          NH.sub.2       CH.sub.3 SO                                         F          NH.sub.2       CH.sub.3 SO.sub.2                                   F          NH.sub.2       CF.sub.3 SO.sub.2                                   F          NH.sub.2       O-phenyl                                            F          NH.sub.2       O-(4-Cl-phenyl)                                     F          NH.sub.2       ClCF.sub.2 O                                        F          NH.sub.2       i-C.sub.3 H.sub.7                                   F          NH.sub.2       CN                                                  Cl         CF.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              Cl         CF.sub.3 (CO)NH                                                                              H                                                   Cl         CF.sub.3 (CO)NH                                                                              F                                                   Cl         CF.sub.3 (CO)NH                                                                              Cl                                                  Cl         CF.sub.3 (CO)NH                                                                              CN                                                  Cl         CF.sub.3 (CO)NH                                                                              CH.sub.3                                            Cl         CF.sub.3 (CO)NH                                                                              CH.sub.3 O                                          Cl         CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   Cl         CF.sub.3 (CO)NH                                                                              CH.sub.3 S                                          Cl         CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   Cl         CF.sub.3 (CO)NH                                                                              benzyl                                              Cl         CF.sub.3 (CO)NH                                                                              CFCF.sub.2                                          Cl         CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     Cl         CF.sub.3 (CO)NH                                                                              cyclopropyl                                         Cl         CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     Cl         CF.sub.3 (CO)NH                                                                              CF.sub.3 O                                          Cl         CF.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         Cl         CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   Cl         CF.sub.3 (CO)NH                                                                              CF.sub.3 S                                          Cl         CF.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         Cl         CF.sub.3 (CO)NH                                                                              CF.sub.3                                            Cl         CF.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         Cl         CF.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   Cl         CF.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   Cl         CF.sub.3 (CO)NH                                                                              O-phenyl                                            Cl         CF.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     Cl         CH.sub.3 NH    O-(3-CF.sub.3 -phenyl)                              Cl         CH.sub.3 NH    H                                                   Cl         CH.sub.3 NH    F                                                   Cl         CH.sub.3 NH    Cl                                                  Cl         CH.sub.3 NH    CN                                                  Cl         CH.sub.3 NH    CH.sub.3                                            Cl         CH.sub.3 NH    CH.sub.3 O                                          Cl         CH.sub.3 NH    C.sub.2 H.sub.5 O                                   Cl         CH.sub.3 NH    CH.sub.3 S                                          Cl         CH.sub.3 NH    C.sub.2 H.sub.5 S                                   Cl         CH.sub.3 NH    benzyl                                              Cl         CH.sub.3 NH    CFCF.sub.2                                          Cl         CH.sub.3 NH    C.sub.2 F.sub.5                                     Cl         CH.sub.3 NH    cyclopropyl                                         Cl         CH.sub.3 NH    C.sub.2 H.sub.5                                     Cl         CH.sub.3 NH    CF.sub.3 O                                          Cl         CH.sub.3 NH    F.sub.2 CHO                                         Cl         CH.sub.3 NH    C.sub.2 F.sub.5 O                                   Cl         CH.sub.3 NH    CF.sub.3 S                                          Cl         CH.sub.3 NH    F.sub.2 CHS                                         Cl         CH.sub.3 NH    CF.sub.3                                            Cl         CH.sub.3 NH    CH.sub.3 SO                                         Cl         CH.sub.3 NH    CH.sub.3 SO.sub.2                                   Cl         CH.sub.3 NH    CF.sub.3 SO.sub.2                                   Cl         CH.sub.3 NH    O-phenyl                                            Cl         CH.sub.3 NH    O-(4-Cl-phenyl)                                     CH.sub.3   CF.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              CH.sub.3   CF.sub.3 (CO)NH                                                                              H                                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              F                                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              Cl                                                  CH.sub.3   CF.sub.3 (CO)NH                                                                              CN                                                  CH.sub.3   CF.sub.3 (CO)NH                                                                              CH.sub.3                                            CH.sub.3   CF.sub.3 (CO)NH                                                                              CH.sub.3 O                                          CH.sub.3   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              CH.sub.3 S                                          CH.sub.3   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              benzyl                                              CH.sub.3   CF.sub.3 (CO)NH                                                                              CFCF.sub.2                                          CH.sub.3   CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     CH.sub.3   CF.sub.3 (CO)NH                                                                              cyclopropyl                                         CH.sub.3   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     CH.sub.3   CF.sub.3 (CO)NH                                                                              CF.sub.3 O                                          CH.sub.3   CF.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         CH.sub.3   CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              CF.sub.3 S                                          CH.sub.3   CF.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         CH.sub.3   CF.sub.3 (CO)NH                                                                              CF.sub.3                                            CH.sub.3   CF.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         CH.sub.3   CF.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   CH.sub.3   CF.sub.3 (CO)NH                                                                              O-phenyl                                            CH.sub.3   CF.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     CH.sub.3 O NH.sub.2       O-(3-CF.sub.3 -phenyl)                              CH.sub.3 O NH.sub.2       H                                                   CH.sub.3 O NH.sub.2       F                                                   CH.sub.3 O NH.sub.2       Cl                                                  CH.sub.3 O NH.sub.2       CN                                                  CH.sub.3 O NH.sub.2       CH.sub.3                                            CH.sub.3 O NH.sub.2       CH.sub.3 O                                          CH.sub.3 O NH.sub.2       C.sub.2 H.sub.5 O                                   CH.sub.3 O NH.sub.2       CH.sub.3 S                                          CH.sub.3 O NH.sub.2       C.sub.2 H.sub.5 S                                   CH.sub.3 O NH.sub.2       benzyl                                              CH.sub.3 O NH.sub.2       CFCF.sub.2                                          CH.sub.3 O NH.sub.2       C.sub.2 F.sub.5                                     CH.sub.3 O NH.sub.2       cyclopropyl                                         CH.sub.3 O NH.sub.2       C.sub.2 H.sub.5                                     CH.sub.3 O NH.sub.2       CF.sub.3 O                                          CH.sub.3 O NH.sub.2       F.sub.2 CHO                                         CH.sub.3 O NH.sub.2       C.sub.2 F.sub.5 O                                   CH.sub.3 O NH.sub.2       CF.sub.3 S                                          CH.sub.3 O NH.sub.2       F.sub.2 CHS                                         CH.sub.3 O NH.sub.2       CF.sub.3                                            CH.sub.3 O NH.sub.2       CH.sub.3 SO                                         CH.sub.3 O NH.sub.2       CH.sub.3 SO.sub.2                                   CH.sub.3 O NH.sub.2       CF.sub.3 SO.sub.2                                   CH.sub.3 O NH.sub.2       O-phenyl                                            CH.sub.3 O NH.sub.2       O-(4-Cl-phenyl)                                     CH.sub.3 O CF.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              CH.sub.3 O CF.sub.3 (CO)NH                                                                              H                                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              F                                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              Cl                                                  CH.sub.3 O CF.sub.3 (CO)NH                                                                              CN                                                  CH.sub.3 O CF.sub.3 (CO)NH                                                                              CH.sub.3                                            CH.sub.3 O CF.sub.3 (CO)NH                                                                              CH.sub.3 O                                          CH.sub.3 O CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              CH.sub.3 S                                          CH.sub.3 O CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              benzyl                                              CH.sub.3 O CF.sub.3 (CO)NH                                                                              CFCF.sub.2                                          CH.sub.3 O CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     CH.sub.3 O CF.sub.3 (CO)NH                                                                              cyclopropyl                                         CH.sub.3 O CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     CH.sub.3 O CF.sub.3 (CO)NH                                                                              CF.sub.3 O                                          CH.sub.3 O CF.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         CH.sub.3 O CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              CF.sub.3 S                                          CH.sub.3 O CF.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         CH.sub.3 O CF.sub.3 (CO)NH                                                                              CF.sub.3                                            CH.sub.3 O CF.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         CH.sub.3 O CF.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   CH.sub.3 O CF.sub.3 (CO)NH                                                                              O-phenyl                                            CH.sub.3 O CF.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     CH.sub.3   NH.sub.2       O-(3-CF.sub.3 -phenyl)                              CH.sub.3   NH.sub.2       H                                                   CH.sub.3   NH.sub.2       F                                                   CH.sub.3   NH.sub.2       Cl                                                  CH.sub.3   NH.sub.2       CN                                                  CH.sub.3   NH.sub.2       CH.sub.3                                            CH.sub.3   NH.sub.2       CH.sub.3 O                                          CH.sub.3   NH.sub.2       C.sub.2 H.sub.5 O                                   CH.sub.3   NH.sub.2       CH.sub.3 S                                          CH.sub.3   NH.sub.2       C.sub.2 H.sub.5 S                                   CH.sub.3   NH.sub.2       benzyl                                              CH.sub.3   NH.sub.2       CFCF.sub.2                                          CH.sub.3   NH.sub.2       C.sub.2 F.sub.5                                     CH.sub.3   NH.sub.2       cyclopropyl                                         CH.sub.3   NH.sub.2       C.sub.2 H.sub.5                                     CH.sub.3   NH.sub.2       CF.sub.3 O                                          CH.sub.3   NH.sub.2       F.sub.2 CHO                                         CH.sub.3   NH.sub.2       C.sub.2 F.sub.5 O                                   CH.sub.3   NH.sub.2       CF.sub.3 S                                          CH.sub.3   NH.sub.2       F.sub.2 CHS                                         CH.sub.3   NH.sub.2       CF.sub.3                                            CH.sub.3   NH.sub.2       CH.sub.3 SO                                         CH.sub.3   NH.sub.2       CH.sub.3 SO.sub.2                                   CH.sub.3   NH.sub.2       CF.sub.3 SO.sub.2                                   CH.sub.3   NH.sub.2       O-phenyl                                            CH.sub.3   NH.sub.2       O-(4-Cl-phenyl)                                     Cl         NH.sub.2       O-(3-CF.sub.3 -phenyl)                              Cl         NH.sub.2       H                                                   Cl         NH.sub.2       F                                                   Cl         NH.sub.2       Cl                                                  Cl         NH.sub.2       CN                                                  Cl         NH.sub.2       CH.sub.3                                            Cl         NH.sub.2       CH.sub.3 O                                          Cl         NH.sub.2       C.sub.2 H.sub.5 O                                   Cl         NH.sub.2       CH.sub.3 S                                          Cl         NH.sub.2       C.sub.2 H.sub.5 S                                   Cl         NH.sub.2       benzyl                                              Cl         NH.sub.2       CFCF.sub.2                                          Cl         NH.sub.2       C.sub.2 F.sub.5                                     Cl         NH.sub.2       cyclopropyl                                         Cl         NH.sub.2       C.sub.2 H.sub.5                                     Cl         NH.sub.2       CF.sub.3 O                                          Cl         NH.sub.2       F.sub.2 CHO                                         Cl         NH.sub.2       C.sub.2 F.sub.5 O                                   Cl         NH.sub.2       CF.sub.3 S                                          Cl         NH.sub.2       F.sub.2 CHS                                         Cl         NH.sub.2       CF.sub.3                                            Cl         NH.sub.2       CH.sub.3 SO                                         Cl         NH.sub.2       CH.sub.3 SO.sub.2                                   Cl         NH.sub.2       CF.sub.3 SO.sub.2                                   Cl         NH.sub.2       O-phenyl                                            Cl         NH.sub.2       O-(4-Cl-phenyl)                                     NH.sub.2   NO.sub.2       O-(3-CF.sub.3 -phenyl)                              NH.sub.2   NO.sub.2       H                                                   NH.sub.2   NO.sub.2       F                                                   NH.sub.2   NO.sub.2       Cl                                                  NH.sub.2   NO.sub.2       CN                                                  NH.sub.2   NO.sub.2       CH.sub.3                                            NH.sub.2   NO.sub.2       CH.sub.3 O                                          NH.sub.2   NO.sub.2       C.sub.2 H.sub.5 O                                   NH.sub.2   NO.sub.2       CH.sub.3 S                                          NH.sub.2   NO.sub.2       C.sub.2 H.sub.5 S                                   NH.sub.2   NO.sub.2       benzyl                                              NH.sub.2   NO.sub.2       CFCF.sub.2                                          NH.sub.2   NO.sub.2       C.sub.2 F.sub.5                                     NH.sub.2   NO.sub.2       cyclopropyl                                         NH.sub.2   NO.sub.2       C.sub.2 H.sub.5                                     NH.sub.2   NO.sub.2       CF.sub.3 O                                          NH.sub.2   NO.sub.2       F.sub.2 CHO                                         NH.sub.2   NO.sub.2       C.sub.2 F.sub.5 O                                   NH.sub.2   NO.sub.2       CF.sub.3 S                                          NH.sub.2   NO.sub.2       F.sub.2 CHS                                         NH.sub.2   NO.sub.2       CF.sub.3                                            NH.sub.2   NO.sub.2       CH.sub.3 SO                                         NH.sub.2   NO.sub.2       CH.sub.3 SO.sub.2                                   NH.sub.2   NO.sub.2       CF.sub.3 SO.sub.2                                   NH.sub.2   NO.sub.2       O-phenyl                                            NH.sub.2   NO.sub.2       O-(4-Cl-phenyl)                                     NH.sub.2   Cl             O-(3-CF.sub.3 -phenyl)                              NH.sub.2   Cl             H                                                   NH.sub.2   Cl             F                                                   NH.sub.2   Cl             Cl                                                  NH.sub.2   Cl             CN                                                  NH.sub.2   Cl             CH.sub.3                                            NH.sub.2   Cl             CH.sub.3 O                                          NH.sub.2   Cl             C.sub.2 H.sub.5 O                                   NH.sub.2   Cl             CH.sub.3 S                                          NH.sub.2   Cl             C.sub.2 H.sub.5 S                                   NH.sub.2   Cl             benzyl                                              NH.sub.2   Cl             CFCF.sub.2                                          NH.sub.2   Cl             C.sub.2 F.sub.5                                     NH.sub.2   Cl             cyclopropyl                                         NH.sub.2   Cl             C.sub.2 H.sub.5                                     NH.sub.2   Cl             CF.sub.3 O                                          NH.sub.2   Cl             F.sub.2 CHO                                         NH.sub.2   Cl             C.sub.2 F.sub.5 O                                   NH.sub.2   Cl             CF.sub.3 S                                          NH.sub.2   Cl             F.sub.2 CHS                                         NH.sub.2   Cl             CF.sub.3                                            NH.sub.2   Cl             CH.sub.3 SO                                         NH.sub.2   Cl             CH.sub.3 SO.sub.2                                   NH.sub.2   Cl             CF.sub.3 SO.sub.2                                   NH.sub.2   Cl             O-phenyl                                            NH.sub.2   Cl             O-(4-Cl-phenyl)                                     NH.sub.2   NH.sub.2       O-(3-CF.sub.3 -phenyl)                              NH.sub.2   NH.sub.2       H                                                   NH.sub.2   NH.sub.2       F                                                   NH.sub.2   NH.sub.2       Cl                                                  NH.sub.2   NH.sub.2       CN                                                  NH.sub.2   NH.sub.2       CH.sub.3                                            NH.sub.2   NH.sub.2       CH.sub.3 O                                          NH.sub.2   NH.sub.2       C.sub.2 H.sub.5 O                                   NH.sub.2   NH.sub.2       CH.sub.3 S                                          NH.sub.2   NH.sub.2       C.sub.2 H.sub.5 S                                   NH.sub.2   NH.sub.2       benzyl                                              NH.sub.2   NH.sub.2       CFCF.sub.2                                          NH.sub.2   NH.sub.2       C.sub.2 F.sub.5                                     NH.sub.2   NH.sub.2       cyclopropyl                                         NH.sub.2   NH.sub.2       C.sub.2 H.sub.5                                     NH.sub.2   NH.sub.2       CF.sub.3 O                                          NH.sub.2   NH.sub.2       F.sub.2 CHO                                         NH.sub.2   NH.sub.2       C.sub.2 F.sub.5 O                                   NH.sub.2   NH.sub.2       CF.sub.3 S                                          NH.sub.2   NH.sub.2       F.sub.2 CHS                                         NH.sub.2   NH.sub.2       CF.sub.3                                            NH.sub.2   NH.sub.2       CH.sub.3 SO                                         NH.sub.2   NH.sub.2       CH.sub.3 SO.sub.2                                   NH.sub.2   NH.sub.2       CF.sub.3 SO.sub.2                                   NH.sub.2   NH.sub.2       O-phenyl                                            NH.sub.2   NH.sub.2       O-(4-Cl-phenyl)                                     NH.sub.2   CF.sub.3 (CO)NH                                                                              O-(3-CF.sub.3 -phenyl)                              NH.sub.2   CF.sub.3 (CO)NH                                                                              H                                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              F                                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              Cl                                                  NH.sub.2   CF.sub.3 (CO)NH                                                                              CN                                                  NH.sub.2   CF.sub.3 (CO)NH                                                                              CH.sub.3                                            NH.sub.2   CF.sub.3 (CO)NH                                                                              CH.sub.3 O                                          NH.sub.2   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 O                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              CH.sub.3 S                                          NH.sub.2   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5 S                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              benzyl                                              NH.sub.2   CF.sub.3 (CO)NH                                                                              CFCF.sub.2                                          NH.sub.2   CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5                                     NH.sub.2   CF.sub.3 (CO)NH                                                                              cyclopropyl                                         NH.sub.2   CF.sub.3 (CO)NH                                                                              C.sub.2 H.sub.5                                     NH.sub.2   CF.sub.3 (CO)NH                                                                              CF.sub.3 O                                          NH.sub.2   CF.sub.3 (CO)NH                                                                              F.sub.2 CHO                                         NH.sub.2   CF.sub.3 (CO)NH                                                                              C.sub.2 F.sub.5 O                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              CF.sub.3 S                                          NH.sub.2   CF.sub.3 (CO)NH                                                                              F.sub.2 CHS                                         NH.sub.2   CF.sub.3 (CO)NH                                                                              CF.sub.3                                            NH.sub.2   CF.sub.3 (CO)NH                                                                              CH.sub.3 SO                                         NH.sub.2   CF.sub.3 (CO)NH                                                                              CH.sub.3 SO.sub.2                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              CF.sub.3 SO.sub.2                                   NH.sub.2   CF.sub.3 (CO)NH                                                                              O-phenyl                                            NH.sub.2   CF.sub.3 (CO)NH                                                                              O-(4-Cl-phenyl)                                     CF.sub.3 (CO)NH                                                                          Cl             O-(3-CF.sub.3 -phenyl)                              CF.sub.3 (CO)NH                                                                          Cl             H                                                   CF.sub.3 (CO)NH                                                                          Cl             F                                                   CF.sub.3 (CO)NH                                                                          Cl             Cl                                                  CF.sub.3 (CO)NH                                                                          Cl             CN                                                  CF.sub.3 (CO)NH                                                                          Cl             CH.sub.3                                            CF.sub.3 (CO)NH                                                                          Cl             CH.sub.3 O                                          CF.sub.3 (CO)NH                                                                          Cl             C.sub.2 H.sub.5 O                                   CF.sub.3 (CO)NH                                                                          Cl             CH.sub.3 S                                          CF.sub.3 (CO)NH                                                                          Cl             C.sub.2 H.sub.5 S                                   CF.sub.3 (CO)NH                                                                          Cl             benzyl                                              CF.sub.3 (CO)NH                                                                          Cl             CFCF.sub.2                                          CF.sub.3 (CO)NH                                                                          Cl             C.sub.2 F.sub.5                                     CF.sub.3 (CO)NH                                                                          Cl             cyclopropyl                                         CF.sub.3 (CO)NH                                                                          Cl             C.sub.2 H.sub.5                                     CF.sub.3 (CO)NH                                                                          Cl             CF.sub.3 O                                          CF.sub.3 (CO)NH                                                                          Cl             F.sub.2 CHO                                         CF.sub.3 (CO)NH                                                                          Cl             C.sub.2 F.sub.5 O                                   CF.sub.3 (CO)NH                                                                          Cl             CF.sub.3 S                                          CF.sub.3 (CO)NH                                                                          Cl             F.sub.2 CHS                                         CF.sub.3 (CO)NH                                                                          Cl             CF.sub.3                                            CF.sub.3 (CO)NH                                                                          Cl             CH.sub.3 SO                                         CF.sub.3 (CO)NH                                                                          Cl             CH.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          Cl             CF.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          Cl             O-phenyl                                            CF.sub.3 (CO)NH                                                                          Cl             O-(4-Cl-phenyl)                                     CF.sub.3 (CO)NH                                                                          CH.sub.3       O-(3-CF.sub.3 -phenyl)                              CF.sub.3 (CO)NH                                                                          CH.sub.3       H                                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       F                                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       Cl                                                  CF.sub.3 (CO)NH                                                                          CH.sub.3       CN                                                  CF.sub.3 (CO)NH                                                                          CH.sub.3       CH.sub.3                                            CF.sub.3 (CO)NH                                                                          CH.sub.3       CH.sub.3 O                                          CF.sub.3 (CO)NH                                                                          CH.sub.3       C.sub.2 H.sub.5 O                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       CH.sub.3 S                                          CF.sub.3 (CO)NH                                                                          CH.sub.3       C.sub.2 H.sub.5 S                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       benzyl                                              CF.sub.3 (CO)NH                                                                          CH.sub.3       CFCF.sub.2                                          CF.sub.3 (CO)NH                                                                          CH.sub.3       C.sub.2 F.sub.5                                     CF.sub.3 (CO)NH                                                                          CH.sub.3       cyclopropyl                                         CF.sub.3 (CO)NH                                                                          CH.sub.3       C.sub.2 H.sub.5                                     CF.sub.3 (CO)NH                                                                          CH.sub.3       CF.sub.3 O                                          CF.sub.3 (CO)NH                                                                          CH.sub.3       F.sub.2 CHO                                         CF.sub.3 (CO)NH                                                                          CH.sub.3       C.sub.2 F.sub.5 O                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       CF.sub.3 S                                          CF.sub.3 (CO)NH                                                                          CH.sub.3       F.sub.2 CHS                                         CF.sub.3 (CO)NH                                                                          CH.sub.3       CF.sub.3                                            CF.sub.3 (CO)NH                                                                          CH.sub.3       CH.sub.3 SO                                         CF.sub.3 (CO)NH                                                                          CH.sub.3       CH.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       CF.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          CH.sub.3       O-phenyl                                            CF.sub.3 (CO)NH                                                                          CH.sub.3       O-(4-Cl-phenyl)                                     CF.sub.3 (CO)NH                                                                          CH.sub.3 O     O-(3-CF.sub.3 -phenyl)                              CF.sub.3 (CO)NH                                                                          CH.sub.3 O     H                                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     F                                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     Cl                                                  CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CN                                                  CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CH.sub.3                                            CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CH.sub.3 O                                          CF.sub.3 (CO)NH                                                                          CH.sub.3 O     C.sub.2 H.sub.5 O                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CH.sub.3 S                                          CF.sub.3 (CO)NH                                                                          CH.sub.3 O     C.sub.2 H.sub.5 S                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     benzyl                                              CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CFCF.sub.2                                          CF.sub.3 (CO)NH                                                                          CH.sub.3 O     C.sub.2 F.sub.5                                     CF.sub.3 (CO)NH                                                                          CH.sub.3 O     cyclopropyl                                         CF.sub.3 (CO)NH                                                                          CH.sub.3 O     C.sub.2 H.sub.5                                     CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CF.sub.3 O                                          CF.sub.3 (CO)NH                                                                          CH.sub.3 O     F.sub.2 CHO                                         CF.sub.3 (CO)NH                                                                          CH.sub.3 O     C.sub.2 F.sub.5 O                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CF.sub.3 S                                          CF.sub.3 (CO)NH                                                                          CH.sub.3 O     F.sub.2 CHS                                         CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CF.sub.3                                            CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CH.sub.3 SO                                         CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CH.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     CF.sub.3 SO.sub.2                                   CF.sub.3 (CO)NH                                                                          CH.sub.3 O     O-phenyl                                            CF.sub.3 (CO)NH                                                                          CH.sub.3 O     O-(4-Cl-phenyl)                                     Cl         Cl             NO.sub.2                                            CH.sub.3   Cl             NO.sub.2                                            Cl         CH.sub.3       NO.sub.2                                            CH.sub.3 O Cl             NO.sub.2                                            Cl         CH.sub.3 O     NO.sub.2                                            CH.sub.3   CH.sub.3       NO.sub.2                                            NH.sub.2   Cl             NO.sub.2                                            CF.sub.3 (CO)NH                                                                          Cl             NO.sub.2                                            Cl         Cl             OH                                                  CH.sub.3   Cl             OH                                                  Cl         CH.sub.3       OH                                                  CH.sub.3   CH.sub.3       OH                                                  CH.sub.3 O Cl             OH                                                  Cl         CH.sub.3 O     OH                                                  Cl         Cl             CH.sub.3 CO.sub.2                                   CH.sub.3   Cl             CH.sub.3 CO.sub.2                                   Cl         CH.sub.3       CH.sub.2 CO.sub.2                                   CH.sub.3   CH.sub.3       CH.sub.3 CO.sub.2                                   CH.sub.3 O Cl             CH.sub.3 CO.sub.2                                   Cl         CH.sub.3 O     CH.sub.3 CO.sub.2                                   CH.sub.3 CO.sub.2                                                                        Cl             Cl                                                  CH.sub.3 CO.sub.2                                                                        CH.sub.3       Cl                                                  CH.sub.3 CO.sub.2                                                                        Cl             CH.sub.3                                            CH.sub.3 CO.sub.2                                                                        Cl             CH.sub.3 O                                          Cl         CH.sub.3 CO.sub.2                                                                            Cl                                                  CH.sub.3   CH.sub.3 CO.sub.2                                                                            Cl                                                  Cl         Cl             CF.sub.3 CO.sub.2                                   Cl         CH.sub.3       CF.sub.3 CO.sub.2                                   Cl         Cl             NH.sub.2                                            CH.sub.3   Cl             NH.sub.2                                            Cl         CH.sub.3       NH.sub.2                                            CH.sub.3   CH.sub.3       NH.sub.2                                            CH.sub.3 O Cl             NH.sub.2                                            Cl         CH.sub.3 O     NH.sub.2                                            Cl         Cl             CF.sub.3 (CO)NH                                     CH.sub.3   Cl             CF.sub.3 (CO)NH                                     Cl         CH.sub.3       CF.sub.3 (CO)NH                                     CH.sub.3 O Cl             CF.sub.3 (CO)NH                                     Cl         CH.sub.3 O     CF.sub.3 (CO)NH                                     CF.sub.3 CO.sub.2                                                                        Cl             H                                                   CF.sub.3 CO.sub.2                                                                        CH.sub.3       H                                                   CF.sub.3 CO.sub.2                                                                        CH.sub.3       Cl                                                  CF.sub.3 CO.sub.2                                                                        Cl             CH.sub.3                                            C.sub.6 H.sub.5 CH.sub.2 NH                                                              H              H                                                   C.sub.6 H.sub.5 CH.sub.2 NH                                                              Cl             H                                                   CH.sub.3   Cl             C.sub.6 H.sub.5 CH.sub.2 NH                         CH.sub.3 O Cl             C.sub.6 H.sub.5 CH.sub.2 NH                         ______________________________________                                    

Preferred definitions of R¹ are:

    ______________________________________                                        No.          R.sup.1                                                          ______________________________________                                        L1           OCH.sub.3                                                        L2           OC.sub.2 H.sub.5                                                 L3           O-i-C.sub.3 H.sub.7                                              L4           n-C.sub.3 H.sub.7                                                L5           i-C.sub.3 H.sub.7                                                L6           n-C.sub.4 H.sub.9                                                L7           i-C.sub.4 H.sub.9                                                L8           sec-C.sub.4 H.sub.9                                              L9           tert-C.sub.4 H.sub.9                                             L10          n-C.sub.5 H.sub.11                                               L11          CH(CH.sub.3)C.sub.3 H.sub.7                                      L12          CH(C.sub.2 H.sub.5)C.sub.2 H.sub.5                               L13          n-C.sub.6 H.sub.13                                               L14          CH(CH.sub.3)C.sub.4 H.sub.9                                      L15          CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                               L16          OC(CH.sub.3).sub.3                                               L17          cyclo-C.sub.3 H.sub.5                                            L18          cyclo-C.sub.4 H.sub.7                                            L19          cyclo-C.sub.5 H.sub.9                                            L20          cyclo-C.sub.6 H.sub.11                                           L21          cyclo-C.sub.7 H.sub.13                                           L22          cyclo-C.sub.8 H.sub.15                                           L23          1-methylcyclohexyl                                               L24          1-ethylcyclohexyl                                                L25          3,5-dimethylcyclohexyl                                           L26          3-trifluoromethyl-                                                            cyclohexyl                                                       L27          1-(cyclopropyl)ethyl                                             L28          1-(cyclopentyl)ethyl                                             L29          1-(cyclohexyl)ethyl                                              L30          CH.sub.2 CHCH.sub.2                                              L31          CH(CH.sub.3)CHCH.sub.2                                           L32          C(CH.sub.3).sub.2 CHCH.sub.2                                     L33          C(CH.sub.3,C.sub.2 H.sub.5)CHCH.sub.2                            L34          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                L35          C(CH.sub.3,C.sub.2 H.sub.5)C.sub.2 H.sub.5                       L36          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                L37          C(CH.sub.3).sub.2 cycloC.sub.6 C.sub.11                          L38          CH.sub.2 C(CH.sub.3)CH.sub.2                                     L39          CH.sub.2 CHCHCH.sub.3                                            L40          CH(CH.sub.3)CHCHCH.sub.3                                         L41          C(CH.sub.3).sub.2 CHCHCH.sub.3                                   L42                                                                                         ##STR30##                                                       L43                                                                                         ##STR31##                                                       L44                                                                                         ##STR32##                                                       L45                                                                                         ##STR33##                                                       L46                                                                                         ##STR34##                                                       L47                                                                                         ##STR35##                                                       L48                                                                                         ##STR36##                                                       L49                                                                                         ##STR37##                                                       L50          CH(CH.sub.3)CH.sub.2 SCH.sub.3                                   L51          C(CH.sub.3).sub.2 CH.sub.2 SCH.sub.3                             L52          CH.sub.2 CH.sub.2 CH.sub.2 SCH.sub.3                             L53          CH(CH.sub.3)CH.sub.2 Cl                                          L54          C(CH.sub.3).sub.2 CH.sub.2 Cl                                    L55          CH(CH.sub.3)CH.sub.2 OCH.sub.3                                   L56          C(CH.sub.3).sub.2 CH.sub.2 OCH.sub.3                             L57          CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                             L58          CH.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                     L59          CH.sub.2 CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2              L60          cyclopropylmethyl                                                L61          C(CH.sub.3).sub.2 CH.sub.2 F                                     L62          H                                                                L63          CH.sub.3                                                         L64          C.sub.2 H.sub.5                                                  L65          1-methylcyclopropyl                                              L66          1-ethylcyclopropyl                                               ______________________________________                                    

The compounds I or the herbicidal compositions containing them and theirenvironmentally tolerable salts e.g. of alkali metals and alkaline earthmetals can very effectively control broadleafed weeds and grass weeds incrops such as wheat, rice, maize, soybeans and cotton without damagingthe crop plants, an effect which occurs especially even at lowapplication rates.

The compounds I or the herbicidal compositions containing them can beapplied by spraying, atomizing, dusting, broadcasting or watering, forexample, in the form of directly sprayable aqueous solutions, powders,suspensions, even high-percentage aqueous, oily or other suspensions ordispersions, emulsions, oil dispersions, pastes, dusting compositions,broadcasting compositions or granules. The application form depend onthe intended uses; in each case they should if possible ensure thefinest dispersion of the active compounds according to the invention.

The compounds I are generally suitable for preparing directly sprayablesolutions, emulsions, pastes or oil dispersions. Suitable inertadditives are mineral oil fractions of medium to high boiling point,such as kerosene or diesel oil, additionally coal tar oils and oils ofvegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons,e.g. paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, alkylated benzenes or their derivatives, methanol, ethanol,propanol, butanol, cyclohexanol, cyclohexanone or strongly polarsolvents, such as N-methylpyrrolidone or water.

Aqueous application forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byaddition of water. To prepare emulsions, pastes or oil dispersions, thesubstrates as such or dissolved in an oil or solvent can be homogenizedin water by means of wetting agents, adhesives, dispersants oremulsifiers. However, concentrates consisting of active substance,wetting agent, adhesive, dispersant or emulsifier and possibly solventor oil can also be prepared, which are suitable for dilution with water.

Suitable surface-active substances are the alkali metal, alkaline earthmetal and ammonium salts of aromatic sulfonic acids, e.g. lignosulfonic,phenolsulfonic, naphthalenesulfonic and dibutylnaphthalenesulfonic acid,as well as of fatty acids, alkyl- and alkylarylsulfonates, alkyl-,lauryl ether and fatty alcohol sulfates, and also salts of sulfatedhexa-, hepta- and octadecanols and of fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and its derivatives withformaldehyde, condensation products of naphthalene or ofnaphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol,alkylphenol or tributylphenol polyglycol ethers, alkylaryl polyetheralcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkylethers, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignin-sulfite waste liquors or methylcellulose.

Powder, broadcasting and dusting compositions can be prepared by mixingor joint grinding of the active substances with a solid carrier.

Granules, e.g. coated, impregnated and homogeneous granules, can beprepared by binding the active compounds to solid carriers. Solidcarriers are mineral earths such as silica gel, silicic acids,silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay,dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such asammonium sulfate, ammonium phosphate, ammonium nitrate, ureas andvegetable products such as cereal flour, tree bark meal, wood meal andnutshell meal, cellulose powder or other solid carriers.

The formulations in general contain from 0.01 to 95% by weight,preferably from 0.5 to 90% by weight, of active compound. The activecompounds are employed here in a purity of from 90% to 100%, preferablyfrom 95% to 100% (by NMR spectrum).

The compounds I according to the invention can be formulated, forexample, as follows:

I. 20 parts by weight of the compound No. 1.001 are dissolved in amixture which consists of 80 parts by weight of alkylated benzene, 10parts by weight of the addition product of from 8 to 10 mol of ethyleneoxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight ofcalcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of theaddition product of 40 mol of ethylene oxide to 1 mol of castor oil. Bypouring out the solution and finely dispersing it in 100,000 parts byweight of water, an aqueous dispersion is obtained which contains 0.02%by weight of the active compound.

II. 20 parts by weight of the compound No. 1.004 are dissolved in amixture which consists of 40 parts-by weight of cyclohexanone, 30 partsby weight of isobutanol, 20 parts by weight of the addition product of 7mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weightof the addition product of 40 mol of ethylene oxide to 1 mol of castoroil. By pouring the solution into and finely dispersing it in 100,000parts by weight of water, an aqueous dispersion is obtained whichcontains 0.02% by weight of the active compound.

III. 20 parts by weight of the active compound No. 1.006 are dissolvedin a mixture which consists of 25 parts by weight of cyclohexanone, 65parts by weight of a mineral oil fraction of boiling point 210° to 280°C. and 10 parts by weight of the addition product of 40 mol of ethyleneoxide to 1 mol of castor oil. By pouring the solution into and finelydispersing it in 100,000 parts by weight of water, an aqueous dispersionis obtained which contains 0.02% by weight of the active compound.

IV. 20 parts by weight of the active compound No. 1.016 are well mixedwith 3 parts by weight of the sodium salt of diisobutylnaphthaleneα-sulfonic acid, 17 parts by weight of the sodium salt of alignosulfonic acid from a sulfite waste liquor and 60 parts by weight ofpowdered silica gel and the mixture is ground in a hammer mill. Byfinely dispersing the mixture in 20,000 parts by weight of water, aspray mixture is obtained which contains 0.1% by weight of the activecompound.

V. 3 parts by weight of the active compound No. 1.018 are mixed with 97parts by weight of finely divided kaolin. In this way a dustingcomposition is obtained which contains 3% by weight of the activecompound.

VI. 20 parts by weight of the active compound No. 1.023 are intimatelymixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonicacid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts byweight of sodium salt of a phenol/urea/formaldehyde condensate and 68parts by weight of a paraffinic mineral oil. A stable oily dispersion isobtained.

The application of the herbicidal compositions or of the activecompounds can be carried out pre-emergence or post-emergence. If theactive compounds are less tolerable for certain crop plants, applicationtechniques can be used in which the herbicidal compositions are sprayedwith the aid of the spray equipment such that the leaves of thesensitive crop plants are not affected if possible, while the activecompounds reach the leaves of undesired plants growing under them or theuncovered soil surface (post-directed, lay-by).

Depending on the target of control, time of year, target plants andstage of growth, the application rates of active compound are from 0.01to 5.0, preferably from 0.05 to 2.0, kg/ha of active substance (a.s.).

In consideration of the variety of application methods, the compounds Iaccording to the invention or compositions containing them canadditionally be employed in a further number of crop plants for theelimination of undesired plants. Suitable crops are, for example, thefollowing:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta,Medicago sativa, Musa spp., Nicotiana tabacum (N. rustica), Oleaeuropaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Piceaabies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyruscommunis, Ribes sylvestre, Ricinus communis, Saccharum officinarum,Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare),Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum,Vicia faba, Vitis vinifera, Zea mays.

To broaden the spectrum of action and to achieve synergistic effects,the pyridine-2,3-dicarboximides I can be mixed and applied together withnumerous representatives of other herbicidal or growth-regulating activecompound groups. For example, suitable herbicidal mixing components arediazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones,2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates, halocarboxylicacids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils,benzofuran derivatives, cyclohexane-1,3-dione derivatives which in the2-position carry, e.g. a carboxyl or carbimino group,quinolinecarboxylic acid derivatives, imidazolines, sulfonamides,sulfonylureas, aryloxy- or heteroaryloxyphenoxypropionic acids and theirsalts, esters and amides and others.

It may additionally be useful to apply the compounds I on their own, ortogether, mixed in a combination with other herbicides or growthregulators and additionally with further crop protection agents, forexample with agents for controlling pests or phytogenic fungi orbacteria. Also of interest is the miscibility with mineral saltsolutions, which can be employed for the elimination of nutritional andtrace element deficiencies. Non-phytotoxic oils and oil concentrates mayalso be added.

A) Preparation of precursors

Diethyl 5-nitropyridine-2,3-dicarboxylate

255 ml of acetic anhydride were added to a mixture of 203.2 g (0.85 mol)of diethyl pyridine-2,3-dicarboxylate-N-oxide in 1.2 l of glacial aceticacid. 68.3 g (1.06 mol) of 98% strength nitric acid were then added inthe course of 40 minutes at from 20° to 28° C. with gentle cooling andstirring and the mixture was stirred at 30° C. for 12 hours. Thereaction solution was poured into 3.5 l of ice-water and extracted withmethylene chloride. The organic phase was extracted in succession withwater, saturated sodium hydrogencarbonate solution and sodium chloridesolution, dried over magnesium sulfate and filtered off with suctionthrough silica gel. After concentration, 177.6 g (78% of theory) ofdiethyl 5-nitropyridine-2,3-dicarboxylate-N-oxide were obtained of n_(D)²⁵ =1.5290. A sample crystallized after relatively long standing; m.p.84°-86° C.

88.8 g (0.648 mol) of phosphorus trichloride were added in the course of30 minutes while stirring at 25° C. to a mixture of 92 g (0.324 mol) ofthe above N-oxide and 300 ml of 1,2-dichloroethane. After stirring at25° C. for 12 hours, the reaction mixture was concentrated in vacuo, theresidue was taken up again in methylene chloride and the solution waspoured into 2.5 l of ice-water. After phase separation, the aqueousphase was extracted with methylene chloride. The organic extract waswashed with water, saturated sodium hydrogencarbonate and sodiumchloride solution, dried over magnesium sulfate and filtered off withsuction through neutral alumina and silica gel. After concentrating,58.2 g (67% of theory) of the title compound were obtained as ayellowish syrup. ¹ H-NMR, 400 MHz (CDCl₃) δ: Ar 9.0 (d/1H), 9.55 (d, 1H)

5-Nitropyridine-2,3-dicarboxylic anhydride

45 g (0.168 mol) of diethyl 5-nitropyridine-2,3-dicarboxylate were addedin the course of 10 minutes with stirring to a mixture of 13.4 g (0.336mol) of sodium hydroxide in 65 ml of water and washed in with 6.5 ml ofethanol. The mixture was brought to reflux, diluted with a further 30 mlof water and cooled again after heating for 1 hour. The precipitatedeposited after the addition of 500 ml of acetone was filtered off withsuction, washed and dried, 42.4 g (98.6% of theory) of sodium5-nitropyridine-2,3-dicarboxylate of m.p.>260° C. being obtained.

This was initially introduced in 500 ml of 1,2-dichloroethane andcombined with 39 g (0.497 mol) of acetyl chloride in the course of 15minutes. The reaction mixture was stirred under reflux for 4 hours andcooled, and the precipitate deposited was separated off and washed withmethylene chloride. After concentrating in vacuo, triturating theresidue with ether/pentane, filtering off with suction and drying, 25.4g (79% of theory) of the title compound of m.p. 85°-91° C. wereobtained.

Diethyl 5-aminopyridine-2,3-dicarboxylate

17 g (0.060 mol) of diethyl 5-nitropyridine-2,3-dicarboxylate-N-oxide in200 ml of glacial acetic acid were added to a mixture of 10.7 g (0.19mol) of iron powder in 50 ml of glacial acetic acid at 70° C. withstirring in the course of 20 minutes. After stirring at 70° C. for 1hour, the reaction mixture was cooled, and the precipitate was filteredoff with suction and washed with ethyl acetate. The filtrate wasconcentrated under reduced pressure, dissolved in methylene chloride,washed with water and with saturated sodium chloride solution, driedover magnesium sulfate and filtered off with suction through silica gel.After concentrating under reduced pressure, 11 g (77% of theory) of thetitle compound were obtained as a semisolid mass.

¹ H-NMR, 270 MHz (CDCl₃) δ: Ar 7.08 (d/l), 8.15 (d, 1), NH₂ 4.45 (s/2)

Diethyl 6-chloro-5-nitropyridine-2,3-dicarboxylate

100 g (0.352 mol) of diethyl 5-nitropyridine-2,3-dicarboxylate wereadded to 500 ml of phosphoryl chloride in the course of 15 minutes withstirring at 60° C., heated to reflux and stirred for 1 1/2 hours. Aftercooling, the reaction mixture was concentrated under reduced pressureand the residue dissolved again in methylene chloride. After stirringwith ice-water, the aqueous phase was washed again with methylenechloride and the organic extracts were then washed in succession withwater, saturated sodium hydrogencarbonate and sodium chloride solutionand dried over magnesium sulfate. After filtering off with suctionthrough neutral alumina and concentrating, 68.8 g (64.6% of theory) ofthe title compound of m.p. 70°-72° C. were obtained. (Not claimedaccording to the invention)

Diethyl 6-benzylaminopyridine-2,3-dicarboxylate

10.7 g (0.1 mol) of benzylamine and 10.1 g (0.1 mol) of triethylaminewere added to a mixture of 25.8 g (0.1 mol) of diethyl6-chloropyridine-2,3-dicarboxylate in 250 ml of propanol at 25° C. withstirring in the course of 10 minutes. After stirring under reflux for 12hours, the reaction mixture was concentrated, the residue was taken upin methylene chloride and the solution was extracted with water. Theorganic phase was dried, filtered off with suction through neutralalumina and concentrated under reduced pressure. The residue was stirredin ether/pentane, filtered off with suction and dried, 23.3 g (71.1% oftheory) of the title compound of m.p. 110°-114° C. being obtained.

Diethyl 5-trifluoroacetamidopyridine-2,3-dicarboxylate

23.8 g (0.114 mol) of trifluoroacetic anhydride were added to a mixtureof 10.8 g (0.045 mol) of diethyl 5-aminopyridine-2,3-dicarboxylate in100 ml of 1,2-dichloroethane with stirring at 25° C. in the course of 10minutes and refluxed for 3 hours. The reaction mixture was introducedinto 500 ml of ice-water and extracted three times with methylenechloride. The organic extract was washed with water, saturated sodiumhydrogencarbonate and a sodium chloride solution and dried overmagnesium sulfate. After concentrating under reduced pressure, 14.6 g(96% of theory) of the title compound were obtained as a colorless syrupof n_(D) ²⁵ =1.5018.

¹ H-NMR, 200 MHz (CDCl₃) δ: Ar 8.63 (s/1), 8.95 (s,1), NH 11.25 (s/1)

B) Preparation of the final products I

N-1-(Cyclopropyl)ethyl-5-nitropyridine-2,3-dicarboximide

11.2 g (0.132 mol) of 1-cyclopropylethylamine were added to a mixture of22.3 g (0.115 mol) of 5-nitropyridine-2,3-dicarboxylic anhydride in 150ml of 1,2-dichloroethane at 25° C. with stirring in the course of 8minutes and the mixture was stirred at 70° C. for 3 hours. After coolingto 25° C., 19.6 g (0.165 mol) of thionyl chloride were added withstirring in the course of 10 minutes and the mixture was stirred at 25°C. for 10 hours and at 70° C. for 1 1/2 hours. The reaction mixture wasdiluted with 100 ml of methylene chloride and added with stirring to 500ml of ice-water. The aqueous phase was extracted twice more withmethylene chloride. The organic phase was then washed successively withwater, saturated sodium hydrogencarbonate and sodium chloride solutionand filtered off with suction over neutral alumina. After concentrating,21.5 g (72% of theory) of the title compound of m.p. 96°-99° C. wereobtained (active compound Example 1.020).

N-tert-Butyl-5-nitropyridine-2,3-dicarboximide

Half of 18 g (0.28 mol) of 98% strength nitric acid and, after 1 hour,the remainder were added in the course of 10 minutes with stirring at20° to 25° C. to a suspension of 53.6 g (0.244 mol) ofN-tert-butylpyridine-2,3-dicarboximide-1-oxide in 150 ml of glacialacetic acid and 71.4 g (0.7 mol) of acetic anhydride and the mixture wasstirred at 25° C. for 16 hours. The reaction mixture was poured into 1.5l of icewater and extracted three times with 300 ml of methylenechloride each time. The organic extract was washed in succession withwater, saturated sodium hydrogencarbonate and sodium chloride solutionand dried over magnesium sulfate. After concentrating in vacuo, 55 g ofa yellow syrup were obtained. This was flash-chromatographed on silicagel using methylene chloride and the middle fraction was concentrated(28 g).

This was initially introduced in 150 ml of 1,2-dichloroethane, treatedwith 28.9 g (0.213 mol) of phosphorus trichloride at 25° C. in thecourse of 10 minutes with stirring and stirred at 75° C for 1 1/2 hours.The reaction mixture was concentrated in vacuo, the residue was taken upin methylene chloride and the solution was stirred into ice-water. Theorganic phase was extracted in succession with water, saturated sodiumhydrogencarbonate and sodium chloride solution and dried over magnesiumsulfate. After filtering off with suction through neutral alumina, thefiltrate was concentrated, and the residue was stirred withether/pentane, filtered off with suction and dried. 20.5 g (33.7% oftheory) of the title compound of m.p. 170°-173° C. were obtained (activecompound Example 1.021).

N-tert-Butyl-6-chloro-5-nitropyridine-2,3-dicarboximide

100 ml of phosphoryl chloride were treated with 7.5 g (0.028 mol) ofN-tert-butyl-5-nitropyridine-2,3-dicarboximide-1-oxide at 60° C. and inportions in the course of 2 minutes with stirring and the mixture wasstirred under reflux for 2 hours. The reaction mixture was concentratedunder reduced pressure, the residue was taken up in methylene chlorideand the solution was stirred into ice-water. The organic phase wasextracted in succession with water, saturated sodium hydrogencarbonateand sodium chloride solution and dried. After filtering off with suctionthrough neutral alumina, it was concentrated and the residue was stirredwith ether and ether/pentane, filtered off with suction and dried. 4.49g (56% of theory) of the title compound of m.p. 100°-104° C. wereobtained (active compound Example 1.019).

N-1-(Cyclopropyl)ethyl-6-amino-5-methylpyridine-2,3-dicarboximide

6.3 g (0.0254 mol) ofN-1-(cyclopropyl)ethyl-6-fluoro-5-methylpyridine-2,3-dicarboximide and4.1 g (0.051 mol) of potassium cyanate were introduced into a mixture of50 ml of DMF and 1 ml of water at 25° C. with stirring and then stirredat 125° C. for 30 minutes. After concentrating the reaction mixtureunder reduced pressure, the residue was stirred in succession withmethyl tert-butyl ether and with water. Insoluble matter was filteredoff with suction, washed with methyl tert-butyl ether and dried underreduced pressure. 3.5 g (56% of theory) of the title compound of m.p.219°-220° C. were obtained. A further 1.6 g (=26% of theory) of thetitle compound of m.p. 201°-219° C. were obtained from the organic phaseafter washing with water and drying over magnesium sulfate (activecompound Example 1.059).

N-tert-Butyl-4-amino-6-chloropyridine- and6-amino-4-chloropyridine-2,3-dicarboximide

14.3 g (0.052 mol) of N-tert-butyl4,6-dichloropyridine-2,3-dicarboximide and 8.5 g (0.105 mol) ofpotassium cyanate were added to a mixture of 100 ml of DMF and 2 ml ofwater at 25° C. and the mixture was stirred at 125° C. for 20 minutes.

After concentrating the reaction mixture under reduced pressure, theresidue was stirred into a mixture of methyl tertbutyl ether and waterand the solid was filtered off with suction. Repeated stirring withmethyl tert-butyl ether, filtering off with suction and drying yielded8.73 g (66% of theory) ofN-tert-butyl-4-amino-6-chloropyridine-2,3-dicarboximide of m.p.232°-234° C. (active compound Example 1.048).

The organic filtrate was washed with water and saturated sodiumchloridesolution, dried over magnesium sulfate and concentrated. The residue wastaken up in methylene chloride and filtered off with suction throughsilica gel, 0.95 g (7.2% of theory) ofN-tert-butyl-6-amino-4-chloropyridine-2,3-dicarboximide of m.p.215°-220° C. being isolated from fractions 3 and 4 (active compoundExample 1.053).

According to these processes described in Examples B and the precursors,the pyridine-2,3-dicarboximides of the formula I listed in Table 1 wereobtained. Novel pyridine-2,3-dicarboxylic anhydrides andpyridine-2,3-dicarboxylic acid esters are listed in Tables 2 and 3.

                                      TABLE 1                                     __________________________________________________________________________     ##STR38##                                                                                                           M.p.                                   No.                                                                              R.sup.1    R.sup.2 R.sup.3  R.sup.4 (°C.)                           __________________________________________________________________________    1.001                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              NO.sub.2 H       118-119                                1.002                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                              NO.sub.2 H       90-91                                  1.003                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                               ##STR39##                                                                             H       162-163                                1.004                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                               ##STR40##                                                                             H       68-71                                  1.005                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              SCN      H       94-95                                  1.006                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              NH.sub.2 H       242                                    1.007                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      NH.sub.2 Cl                                             1.008                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                               ##STR41##                                                                             H       116-117                                1.009                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                              NH.sub.2 H       217-221                                1.010                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                              SCN      H       78-80                                  1.011                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                               ##STR42##                                                                             H       160-161                                1.012                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                              SCN      H        98-100                                1.013                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                               ##STR43##                                                                             H       64-65                                  1.014                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                               ##STR44##                                                                             H       178-179                                1.015                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                              NH.sub.2 H       170-171                                1.016                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                              NO.sub.2 H       n.sub.D.sup.23 = 1.5670                1.017                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                              CH.sub.3 SO.sub.2 NH                                                                   H       158-160                                1.018                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              CH.sub.3 SO.sub.2 NH                                                                   H       149-153                                1.019                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      NO.sub.2 H       100-104                                1.020                                                                            1-(Cyclopropyl)ethyl                                                                     H       NO.sub.2 H       96-99                                  1.021                                                                            tert-C.sub.4 H.sub.9                                                                     H       NO.sub.2 H       170-173                                1.022                                                                            i-C.sub.3 H.sub.7                                                                        H       NO.sub.2 H       166-169                                1.023                                                                            1-(Cyclopropyl)ethyl                                                                     Cl      NO.sub.2 H       65-66                                  1.024                                                                            tert-C.sub.4 H.sub.9                                                                     H                                                                                      ##STR45##                                                                             H       142-145                                1.025                                                                            1-(Cyclopropyl)ethyl                                                                     C.sub.6 H.sub.5 CH.sub.2 NH                                                           H        H       144-148                                1.026                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              CH.sub.3 NH.sub.2                                       1.027                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                              CH.sub.3 NH.sub.2                                       1.028                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              CH.sub.3 NO.sub.2                                       1.029                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              CH.sub.3 OH                                             1.030                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      CH.sub.3 NH.sub.2                                       1.031                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3                                                                              Cl       NH.sub.2                                       1.032                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3 O                                                                            Cl       NH.sub.2                                       1.033                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3 O                                                                            Cl       NH.sub.2                                       1.034                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              Cl       OH                                             1.035                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3 O                                                                            Cl       OH                                             1.036                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      Cl       NH.sub.2                                                                              232-234                                1.037                                                                            1-(Cyclopropyl)ethyl                                                                     Cl      Cl       NH.sub.2                                       1.038                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      Cl       CF.sub.3 (CO)NH                                1.039                                                                            tert-C.sub.4 H.sub.9                                                                      ##STR46##                                                                            CH.sub.3 H       159-160                                1.040                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              CH.sub.3 H       286-290                                1.041                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              CH.sub.3 O                                                                             H       220-225                                1.042                                                                            tert-C.sub.4 H.sub.9                                                                      ##STR47##                                                                            H        H       151-154                                1.043                                                                            tert-C.sub.4 H.sub.9                                                                     H                                                                                      ##STR48##                                                                             H       193-195                                1.044                                                                            tert-C.sub.4 H.sub.9                                                                     H       NH.sub.2 H       187-190                                1.045                                                                            tert-C.sub.4 H.sub.9                                                                      ##STR49##                                                                            Cl       H       168-171                                1.046                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              Cl       H       258-260                                1.047                                                                            i-C.sub.3 H.sub.7                                                                        Cl      Cl       NH.sub.2                                                                              249-253                                1.048                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      H        NH.sub.2                                                                              232-234                                1.049                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              Cl       Cl      215-220                                1.050                                                                            tert-C.sub.4 H.sub.9                                                                      ##STR50##                                                                            CH.sub.3 O                                                                             H       245-248                                1.051                                                                            i-C.sub.3 H.sub.7                                                                        Cl                                                                                     ##STR51##                                                                             H       145-148                                1.052                                                                            tert-C.sub.4 H.sub.9                                                                     Cl                                                                                     ##STR52##                                                                             H       124-127                                1.053                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              H        Cl      215-220                                1.054                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      Cl                                                                                      ##STR53##                                                                            135-137                                1.055                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      H                                                                                       ##STR54##                                                                            136-139                                1.056                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      H                                                                                       ##STR55##                                                                            105-106                                1.057                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      CH.sub.3 O                                                                             NH.sub.2                                                                              212-215                                1.058                                                                            1-(Cyclopropyl)ethyl                                                                      ##STR56##                                                                            CH.sub.3 H       170172                                 1.059                                                                            1-(Cyclopropyl)ethyl                                                                     NH.sub.2                                                                              CH.sub.3 H       219-220                                1.060                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                               ##STR57##                                                                             H       174-175                                1.061                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3 O                                                                             ##STR58##                                                                             H       185-187                                1.062                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3 O                                                                             ##STR59##                                                                             H       >280                                   1.063                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3 O                                                                            NH.sub.2 H       200-202                                1.064                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3 O                                                                            NO.sub.2 H       140-141                                1.065                                                                            tert-C.sub.4H.sub.9                                                                      NH.sub.2                                                                              H        H       179-182                                1.066                                                                            i-C.sub.3 H.sub.7                                                                        NH.sub.2                                                                              H        H       153-157                                1.067                                                                            i-C.sub.3 H.sub.7                                                                        NH.sub.2                                                                              CH.sub.3 H       255-260                                1.068                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3 O                                                                            NO.sub.2 H       128-131                                1.069                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3 O                                                                            NO.sub.2 H       152-154                                1.070                                                                            tert-C.sub.4 H.sub.9                                                                     CH.sub.3                                                                              Cl       NH.sub.2                                                                              220-221                                1.071                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3 O                                                                            NH.sub.2 H       213-214                                1.072                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3 O                                                                            NH.sub.2 H       163-165                                1.073                                                                            1-(Cyclopropyl)ethyl                                                                     Cl      CH.sub.3 NH.sub.2                                                                              236-238                                1.074                                                                            1-(Cyclopropyl)ethyl                                                                     NH.sub.2                                                                              CH.sub.3 Cl      234-236                                1.075                                                                            i-C.sub.3 H.sub.7                                                                        Cl      CH.sub.3 NH.sub.2                                                                              >305                                   1.076                                                                            i-C.sub.3 H.sub.7                                                                        NH.sub.2                                                                              CH.sub.3 Cl      298-302                                1.077                                                                            i-C.sub.3 H.sub.7                                                                        CH.sub.3 O                                                                             ##STR60##                                                                             H       178-180                                1.078                                                                            1-(Cyclopropyl)ethyl                                                                     CH.sub.3 O                                                                             ##STR61##                                                                             H       134-136                                1.079                                                                            1-(Cyclopropyl)ethyl                                                                     Cl      CH.sub.3                                                                                ##STR62##                                                                            162-163                                1.080                                                                            i-C.sub.3 H.sub.7                                                                        Cl      CH.sub.3                                                                                ##STR63##                                                                            155-157                                1.081                                                                            1-(Cyclopropyl)ethyl                                                                      ##STR64##                                                                            CH.sub.3 Cl      81-83                                  1.082                                                                            i-C.sub.3 H.sub.7                                                                         ##STR65##                                                                            CH.sub.3 Cl      111-114                                1.083                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      CH.sub.3 NH.sub.2                                                                              253-257                                1.084                                                                            tert-C.sub.4 H.sub.9                                                                     NH.sub.2                                                                              CH.sub.3 Cl      215-217                                1.085                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      CH.sub.3                                                                                ##STR66##                                                                            172-174                                1.086                                                                            tert-C.sub.4 H.sub.9                                                                      ##STR67##                                                                            CH.sub.3 Cl      85-88                                  1.087                                                                            tert-C.sub.4 H.sub.9                                                                     Cl      NH.sub.2 H       240-242                                1.088                                                                            tert-C.sub.4 H.sub.9                                                                     Cl                                                                                     ##STR68##                                                                             H       144-147                                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR69##                                                                                                  Physical data -                                                               M.p. (°C.)                                                             .sup.1 H-NMR, 200 MHz,                          No.                                                                              R.sup.2    R.sup.3 R.sup.4 δ [ppm] in CDCl.sub.3                     __________________________________________________________________________    2.001                                                                            H          NO.sub.2                                                                              H       85-91                                           2.002                                                                            Cl         NO.sub.2                                                                              H                                                       2.003                                                                            Cl         NO.sub.2                                                                              Cl                                                      2.004                                                                            CH.sub.3   NO.sub.2                                                                              H       CH.sub.3 : 3.05 (s/3),                                                        Ar: 8.05 (s/1)                                  2.005                                                                            CH.sub.3   NO.sub.2                                                                              Cl                                                      2.006                                                                            H          NH.sub.2                                                                              H                                                       2.007                                                                            H          CF.sub.3 (CO)NH                                                                       H       153-156                                         2.008                                                                            NH.sub.2   H       H                                                       2.009                                                                            C.sub.6 H.sub.5CH.sub.2 NH                                                               H       H                                                       2.010                                                                             ##STR70## H       H       105-107                                         2.011                                                                            CH.sub.3 O NO.sub.2                                                                              H       123-127                                         2.012                                                                            CH.sub.3 O NH.sub.2                                                                              H                                                       2.013                                                                            CH.sub.3 O CF.sub.3 (CO)NH                                                                       H                                                       2.014                                                                            CF.sub.3 (CO)NH                                                                          H       H                                                       2.015                                                                            Cl         H       CH.sub.3 (CO)NH                                         __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR71##                                                                                                          Physical data-                                                                M.p. (°C.)                                                             .sup.1 H-NMR, 270                                                             MHz, δ                                                                  [ppm] in                                No.  R.sup.2    R.sup.3     R.sup.4                                                                            R.sup.5                                                                            CDCl.sub.3                              ______________________________________                                        3.001                                                                              H          NO.sub.2    H    C.sub.2 H.sub.5                                                                    n.sub.D.sup.25 = 1.5290                 3.002                                                                              Cl         NO.sub.2    H    CH.sub.3                                                                           68-73                                   3.003                                                                              Cl         NO.sub.2    Cl   C.sub.2 H.sub.5                              3.004                                                                              CH.sub.3   NO.sub.2    Cl   CH.sub.3                                     3.005                                                                              H          NH.sub.2    H    C.sub.2 H.sub.5                                                                    Ar:                                                                           7.08 (d/1),                                                                   8.15 (d/1),                                                                   NH.sub.2 : 4.45                                                               (s/2)                                   3.006                                                                              H          CF.sub.3 (CO)NH                                                                           H    C.sub.2 H.sub.5                                                                    n.sub.D.sup.25 = 1.5018                 3.007                                                                              NH.sub.2   H           H    CH.sub.3                                     3.008                                                                              C.sub.6 H.sub.5 CH.sub.2 NH                                                              H           H    C.sub.2 H.sub.5                                                                    110-114                                 3.009                                                                              C.sub.6 H.sub.5 CH.sub.2                                                                 Cl          H    C.sub.2 H.sub.5                              3.010                                                                              CH.sub.3 O NO.sub.2    H    C.sub.2 H.sub.5                                                                    60-64                                   3.011                                                                              CH.sub.3 O NH.sub.2    H    CH.sub.3                                     3.012                                                                              CH.sub.3 O CF.sub.3 (CO)NH                                                                           H    CH.sub.3                                     3.013                                                                              Cl         NH.sub.2    H    C.sub.2 H.sub.5                              3.014                                                                              NH         Cl          H    C.sub.2 H.sub.5                              3.015                                                                              CH.sub.3 O H           NH.sub.2                                                                           CH.sub.3                                     3.016                                                                              Cl         H           NH.sub.2                                                                           CH.sub.3                                     3.017                                                                              Cl         NH.sub.2    H    CH.sub.3                                                                            94-100                                 3.018                                                                              CH.sub.3 O NO.sub.2    H    CH.sub.3                                                                           57-58                                   3.019                                                                              NH.sub.2   H           H    C.sub.2 H.sub.5                                                                    149-155                                 3.020                                                                              Cl         NO.sub.2    H    C.sub.2 H.sub.5                                                                    70-72                                   3.021                                                                              Cl         NO.sub.2    H    CH.sub.3                                                                           ArCH.sub.3                                                                    8.78 (s/1)                              3.022                                                                              CH.sub.3   NO.sub.2    H    CH.sub.3                                                                           60-64                                   ______________________________________                                    

Use examples

It was possible to show the herbicidal action of thepyridine-2,3-dicarboximides of the formula I by greenhouse tests:

The cultivation containers used were plastic pots containing loamy sandcontaining approximately 3.0% of humus as a substrate. The seeds of thetest plants were sown separately according to species.

In the case of pre-emergence treatment, the active compounds suspendedor emulsified in water were applied immediately after sowing by means offinely dispersing nozzles. The containers were lightly watered in orderto promote germination and growth and then covered with transparentplastic hoods until the plants had taken root. This covering causesuniform germination of the test plants if this has not been adverselyaffected by the active compounds.

For the purpose of post-emergence treatment, the test plants were firstraised to a growth height of 3 to 15 cm depending on growth form andonly then treated with the active compounds suspended or emulsified inwater. For this purpose, the test plants were either sown directly andthen raised in the same containers or they were first raised separatelyas seed plants and transplanted into the test containers a few daysbefore treatment. The application rate for post-emergence applicationwas 0.5 or 0.25 kg/ha of a.s.

The plants were kept species-specifically at from 10°-25° C. or 20°-35°C. The test period extended over 2 to 4 weeks. During this time, theplants were tended and their reaction to the individual treatments wasassessed.

The herbicidal action was graded on a scale of from 0 to 100. 100 inthis case means no emergence of the plants or complete destruction of atleast the above-ground parts and 0 means no damage or normal course ofgrowth.

The plants used in the greenhouse tests were made up of the followingspecies:

    ______________________________________                                        Abbreviation                                                                            Botanical name                                                                              Common name                                           ______________________________________                                        CHEAL     Chenopodium album                                                                           Common lamb's-quarters                                POLPE     Polygonum persicaria                                                                        Lady's-thumb                                          SOLNI     Solanum nigrum                                                                              Black nightshade                                      ______________________________________                                    

The results (see following Table I) show the superior herbicidal actionof the compounds according to the invention compared with the comparisonExample A known from EP-A 422 456.

                  TABLE I                                                         ______________________________________                                        Examples of the control of undesired plants on post-emergence                 application of 0.5 kg and 0.25 kg of a.s./ha in a greenhouse                   ##STR72##                                                                    ______________________________________                                        R.sup.3       NH.sub.2                                                                              NH.sub.2 H      H                                       R.sup.2       CH.sub.3                                                                              CH.sub.3 CH.sub.3                                                                             CH.sub.3                                Ex. No.       1.015   1.015    A      A                                       Application rate                                                                            0.5     0.25     0.5    0.25                                    (kg of a.s./ha)                                                               Test plants   Damage in %                                                     CHEAL         100     90       100    75                                      POLPE         100     100      100    60                                      SOLNI         100     100      90     10                                      ______________________________________                                    

We claim:
 1. A pyridine- 2,3-dicarboximide of the general formula I##STR73## where R¹ is hydrogen;C₁ -C₄ -alkoxy; C₁ -C₆ -alkyl which cancarry one to three of the following groups: C₁ -C₄ -alkoxy, C₁ -C₄-haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkylthio, C₁ -C₄-dialkylamino, C₃ -C₈ -cycloalkyl, halogen, excluding C₁ -C₄-dialkylaminoethyl if one of the radicals R², R³ or R⁴ is amino orhydroxyl; C₃ -C₈ -cycloalkyl, which can carry one to three of thefollowing groups: C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkoxy, halogen or nitro; C₃ -C₆ -alkenyl or C₃ -C₆ -alkynyl,which can be substituted up to three times by halogen, and at least oneradical R², R³ or R⁴ is nitro, a group OR⁵ or a group NR⁶ R⁷ and theother radicals R², R³ and R⁴ are defined as follows:i) hydrogen; ii)halogen, nitro or cyano; iii) C₁ -C₆ -alkyl, which can be substituted byone to five halogen atoms and/or one or two of the following radicals:C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkylthio, C₃ -C₆ -cycloalkyl or cyano; iv) benzyl which can besubstituted up to three times by C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkylthio, halogen, cyano or nitro; v) C₃ -C₈ -cycloalkyl which canbe substituted one to three times by C₁ -C₄ -alkyl or halogen; vi) C₂-C₆ -alkenyl which can be substituted up to three times by halogenand/or once by C₁ -C₃ -alkoxy or by phenyl which can carry one to threeof the following groups: C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkylthio,halogen, cyano or nitro; vii) C₂ -C₆ -alkynyl which can be substitutedup to three times by halogen or C₁ -C₃ -alkoxy and/or once by phenylwhich can carry one to three of the following groups: C₁ -C₄ -alkyl, C₁-C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio,C₁ -C₄ -haloalkylthio, halogen, cyano or nitro; viii) C₁ -C₄ -alkoxy, C₁-C₄ -alkylthio, C₁ -C₄ -haloalkoxy, C₁ -C₄ -haloalkylthio, C₂ -C₅-alkenyloxy, C₂ -C₅ -alkynyloxy, C₁ -C₄ -alkylsulfinyl, C₁ -C₄-alkylsulfonyl, C₁ -C₄ -haloalkylsulfonyl; ix) phenoxy or phenylthiowhich can be substituted up to three times by C₁ -C₄ -alkyl, C₁ -C₄-haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio, C₁-C₄ -haloalkylthio, halogen, cyano or nitro; x) a 5- or 6-memberedheterocyclic radical having one or two heteroatoms selected from thegroup consisting of oxygen, sulfur and nitrogen which can carry one ortwo of the following groups: C₁ -C₃ -alkyl, halogen, C₁ -C₃ -alkoxy orC₂ -C₄ -alkoxycarbonyl; xi) phenyl which can carry one to three of thefollowing groups: C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkoxy, C₁-C₆ -haloalkoxy, C₁ -C₆ -alkylthio, C₁ -C₆ -haloalkylthio, halogen,nitro or cyano; xii ) a group OR⁵, where R⁵ is hydrogen, C₁ -C₄-alkylcarbonyl, C₁ -C₄ -haloalkylcarbonyl, C₁ -C₄ -alkoxycarbonyl, C₁-C₄ -alkoxy-C₂ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylcarbamoyl, C₁ -C₄-dialkylcarbamoyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄ -haloalkylsulfonyl,sulfamoyl, C₁ -C₄ -alkylaminosulfonyl, C₁ -C₄ -dialkylaminosulfonyl,phenylsulfonyl, which can be substituted one to three times by C₁ -C₄-alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄-alkylthio, halogen, cyano or nitro; xiii) a group NR⁶ R⁷, where R⁶ ishydrogen, C₁ -C₄ -alkyl, benzyl, C₁ -C₄ -alkoxy or, together with R⁷, isC═S and R⁷ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄-haloalkylcarbonyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy-C₂ -C₄-alkoxycarbonyl, C₁ -C₄ -alkylcarbamoyl, C₁ -C₄ -dialkylcarbamoyl, C₁-C₄ -alkylsulfonyl, C₁ -C₄ -haloalkylsulfonyl, sulfamoyl, C₁ -C₄-alkylaminosulfonyl, C₁ -C₄ -dialkylaminosulfonyl, phenylsulfonyl, whichcan be substituted one to three times by C₁ -C₄ -alkyl, C₁ -C₄-haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio,halogen, cyano or nitro; excluding6-amino-5-cyano-4-phenylpyridine-2,3-dicarboximide; or itsagriculturally utilizable salts.
 2. A pyridine-2,3-dicarboximide of theformula I as claimed in claim 1, where the substituents have thefollowing meanings:R¹ is C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆-alkynyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-(cyclopropyl)-C₁-C₃ -alkyl or C₃ -C₆ -cycloalkyl; two of the three radicals R², R³ andR⁴ independently of one another are hydrogen, C₁ -C₄ -alkyl which can besubstituted by one to five halogen atoms, C₁ -C₄ -alkoxy, halogen orcyano and the third radical is as mentioned in claim
 1. 3. Apyridine-2,3-dicarboximide of the formula I as defined in claim 1, whereR² and/or R³ and/or R⁴ are nitro.
 4. A herbicidal composition,containing a herbicidally effective amount of apyridine-2,3-dicarboximide of the formula I as defined in claim 1, orits salt, and carriers customary therefor.
 5. A method of controllingundesired plant growth, which comprises treating the undesired plantsand/or their habitat with a herbicidally effective amount of apyridine-2,3-dicarboximide of the formula I as defined in claim
 1. 6. Apyridine-2,3-dicarboximide of the formula I as defined in claim 2, whereR² and/or R³ and/or R⁴ are nitro.
 7. A herbicidal composition,containing a herbicidally, effective amount of apyridine-2,3-dicarboximide of the formula I as defined in claim 6, orits salt, and carriers customary therefor.
 8. Apyridine-2,3-dicarboximide of the formula I as defined in claim 1,wherein R¹ is t-butyl, R² is methyl, R³ is nitro and R⁴ is hydrogen. 9.A method of controlling undesirable plant growth in wheat whichcomprises treating the undesirable plants and/or their habitat with aherbicidally effective amount of a pyridine-2,3-dicarboximide as definedin claim 8.